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					FUELS
The discussion relates to fossil or chemical fuels Definition Fuel is a carbonaceous combustible substance, which on combustion liberates a large amount of energy in the form of heat. Classification On the basis of occurrence, fuels are classified as primary and secondary fuels  Primary fuels occur in nature and are used without processing.  Secondary fuels are obtained by chemical processing of primary fuels. On the basis of physical state, fuels are classified as solid, liquid and gaseous fuels

Fuels
Primary Solid
E.g. Coal Wood

Secondary

Liquid
Crude oil (Petroleum)

Gaseous
Natural gas

Solid
Charcoal Coke

Liquid
Petrol Diesel

Gaseous
Coal gas Water gas

Calorific Value The quality of a fuel is determined by the amount of energy released per unit mass or volume referred to as calorific value. Definition  Calorific value of a fuel is the amount of heat liberated when a unit mass or a unit volume of the fuel is burnt completely in air or oxygen.  Fuels generally contain hydrogen in addition to carbon. During combustion, the hydrogen is converted to steam.  In the determination of calorific value of the fuel if the products of combustion are cooled to ambient temperature (room temperature), the latent heat of steam is also included. This is referred to as gross calorific value (GCV) or higher calorific value.  In practice, the products of combustion are allowed to escape and the amount of heat realized is lesser than the GCV (since the latent heat of vaporization is not released). This is net calorific value (NCV) or lower calorific value. GCV  = NCV + latent heat of steam

Gross Calorific value is the amount of heat liberated when a unit mass or a unit volume of the fuel is burnt completely in air or oxygen and the products of combustion are cooled to ambient temperature.

Notes by Maheshwara Reddy , Dayaynanda Sagar College of Engineering, Bangalore

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Net Calorific value is the amount of heat liberated when a unit mass or a unit volume of the fuel is burnt completely in air or oxygen and the products of combustion are allowed to escape.

Determination of Calorific Value of a Solid Fuel - Bomb Calorimeter
Oxygen

B

Stirrer

Wires for ignition

Thermometer Lid

A

Sample

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Construction The bomb calorimeter (shown in the fig.) consists of an outer cylindrical steel vessel (bomb) with an airtight screw and an inlet for oxygen. The bomb has a platinum crucible with a loop of wire. The ends of the wire project out and can be connected to a source of electric current. The bomb is immersed in a rectangular vessel (calorimeter) containing water, which is continuously stirred. A Beckmann thermometer is introduced into the calorimeter.

Working  A known mass of the fuel is made into a pellet and taken in the crucible.  Oxygen is passed through the bomb.  A known mass of water is taken in the calorimeter and is closed with the lid.  The initial temperature of water is noted.  The ends of the wire are connected to an electric source so as to ignite the fuel.  The heat released is absorbed by water. The temperature of water rises.  The final temperature is noted.
Notes by Maheshwara Reddy , Dayaynanda Sagar College of Engineering, Bangalore

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Calculation Let m = mass of fuel W = mass of water w = water equivalent of calorimeter t1 = initial temperature of water t2 = final temperature of water s = specific heat of water GCV ( solid fuel) = (W+w)  (t2-t1)  s m

If the fuel contains x% hydrogen, NCV of the fuel is calculated as follows 2 atoms of hydrogen produce one molecule of water 2g of hydrogen produce 18 g of water x g of hydrogen produce 9 g of water x % hydrogen  9  x g of water = 0.09  x g of water 100 NCV = GCV - latent heat of steam formed = GCV - 0.09  x  latent heat of steam Latent heat of steam = 2454 kJ kg-1 1 calorie = 4.187 kJ kg-1 The calorific value of a liquid fuel can be determined using bomb calorimeter.

Notes by Maheshwara Reddy , Dayaynanda Sagar College of Engineering, Bangalore

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Determination of Calorific Value of a Gaseous Fuel - Boy’s Calorimeter

T2 Gas Exit Water outlet

T1

Water inlet

Condenser for cooling water vapour formed during the combustion Condenser outlet

Tubes for circulating water Combustion chamber of the calorimeter Gas meter

Gas inlet Burner

Construction  Boy‘s calorimeter (shown in fig.) consists of a combustion chamber surrounded by water tube with two thermometers T1 and T2 attached.  There is a burner in the chamber, which is connected to a gas tube. Working  A known volume of water is passed through the tubes.  The initial temperature is noted when the two thermometers show the same constant temperature.  A known volume of the gas (measured using a meter) is passed through the tube and burnt in the combustion chamber.  The heat liberated is absorbed by the water in the tubes.  The final temperature of water is noted.  The gaseous products are cooled and condensed into a measuring jar.

Calculation: Let V = volume of gas burnt W = mass of water t1 = initial temperature of water
Notes by Maheshwara Reddy , Dayaynanda Sagar College of Engineering, Bangalore

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t2 = final temperature of water s = specific heat of water v = volume of water collected in the measuring jar W  s  (t2- t1) V NCV ( gaseous fuel) = GCV - latent heat of steam formed = GCV - latent heat of steam  volume of water collected. GCV( gaseous fuel) = Formulae for Solving Numerical Problems:     GCV (solid fuel) = (W+w)  (t2-t1)  s m = GCV - latent heat = G.C.V. - (0.09  % of H)  latent heat

NCV (solid fuel)

W  s  (t2- t1) V NCV ( gaseous fuel) = GCV – latent heat = G.C.V. – amount of water collected  latent heat V = G.C.V. – v  latent heat V (1 cm3 of water  1 g of water) GCV( gaseous fuel) =

Numerical Problems Problem 1: Calculate the gross calorific value and net calorific value of a sample of coal 0. 5g of which when burnt in a bomb calorimeter, raised the temperature of 1000g of water from 293K to 301.6K. The water equivalent of calorimeter is 350 g. The specific heat of water is 4.187 kJ kg-1, latent heat of steam is 2457.2kJkg-1. the coal sample contains 93% carbon, 5% hydrogen and 2% ash. m = mass of the fuel W = mass of water taken w = water equivalent of calorimeter t1 = initial temperature of water t2 = final temperature of water s = specific heat of water GCV (solid fuel) = (W+w)  (t2-t1)  s m = 0.5 g = 1000 g = 350 g = 293 K = 296.4 K = 4.187 kJ kg-1K-1

= (1000 +350) g  (296.4 -293)K  4.187 kJ kg-1K-1
Notes by Maheshwara Reddy , Dayaynanda Sagar College of Engineering, Bangalore

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0.5g 1350 g  3.4 K  4.187 kJ kg-1K-1 0. 5g = 3 8437 kJ kg-1 = NCV (solid fuel) = = = = = GCV - latent heat G.C.V. - (0.09  % of H)  latent heat 38437 kJ kg-1 - (0.09  5)  1105.7 kJ kg-1 38437 kJ kg-1 – 1106 kJ kg-1 37331 kJ kg-1

Problem 2: Calculate the gross calorific value and net calorific value of a gaseous fuel, 0.012m3 of which when burnt raised the temperature of 3.5kg of water by 8.2K. Specific heat of water is 4.2 kJ kg-1K-1. Latent heat of steam is 2.45 kJ kg-1. The volume of water collected is 6.5cm3 . Latent heat of steam is 2457.2kJ kg-1 V = volume of the gas burnt = 0.015 m3 W = mass of water = 3.5 kg t2- t1 = rise in temperature = 15.6 K s = specific heat of water = 4.2kJ kg-1K-1 v = volume of water collected = 6.5 cm3 GCV( gaseous fuel) = W  s  (t2- t1) V = 3.5 kg  4.2 kJkg-1K-1  15.6 K 0.012m3 = 11073 kJm-3 NCV( gaseous fuel) = GCV – latent heat = G.C.V. - amount of water collected  latent heat V -3 = 11073 kJm – 6.5  10-3 kg  2457.2kJkg-1 0.012 3 (1 cm of water  1 g of water) = 11073 kJm-3 – 6.5  10-3 kg  2457.2kJkg-1 0.015 -3 -3 = 11073 kJm – 1065 kJm = 10008 kJm-3 Cracking of Petroleum  Heavy oil is a major fraction of petroleum refining. It is converted to petrol by cracking. Definition:
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Cracking is the breaking down of high boiling high molecular mass petroleum fractions ( heavy oil) into smaller fragments.

Fluidized Catalytic Cracking  Heavy oil is cracked using zeolite (Y type) catalyst with a rare earth oxide.  Heavy oil is heated to about 580K in a preheater and passed through a riser column(shown in fig.) into a reactor.
To fractionating column

Flue gases

Stripper

Reactor Regenerator Steam Riser column Air Steam / oil

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The reactor contains finely powdered catalyst maintained at about 970K. The heavy oil undergoes cracking. The temperature falls to about 8200K. The cracked product is fractionated to give petrol.

Regeneration of Catalyst  After some time, the catalyst gets deactivated due to the deposition of carbon and oil on its surface.  Steam is passed through the riser column.  The deactivated catalyst is led into a regenerator through which air is passed.  Air oxidizes C to CO2 and steam removes the oil. Reforming of Petrol  Reforming is a process carried out to improve the octane number of petrol by bringing about changes in the structure of hydrocarbons.  The changes in structure could be isomerization, cyclization or aromatization..
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Isomerization straight chain hydrocarbons are converted to branched hydrocarbons

CH3 - CH2 - CH2 - CH2 - CH2 - CH2 - CH3  CH3 - CH - CH2 - CH2 - CH2 - CH3 n- heptane CH3 methyl hexane  Cyclization straight chain hydrocarbons are converted to cyclic compounds

CH3 - CH2 - CH2 - CH2 - CH2 - CH2 - CH3  - CH3 n- heptane methyl cyclohexane  Aromatization cyclic compounds are dehydrogenated. - CH3 methyl cyclohexane  CH3

toluene

Reforming is carried out by passing the petrol through Pt supported on alumina at about 5000C and 50 kg cm-2 pressure.

Knocking in IC Engines  The power output and efficiency of an IC engine depends on the Compression ratio which is the ratio of the volume of the cylinder at the end of the suction stroke to the volume of the cylinder at the end of the compression stroke. Volume of cylinder at end of suction stroke Compression ratio = Volume of cylinder at end of compression stroke       Under ideal conditions, in an IC engine the petrol-air mixture drawn into the cylinder of the engine undergoes compression and then ignited. The hydrocarbons in petrol undergo complete combustion and the flame propagates smoothly. Sometimes, due to deposits of carbon on the walls of the cylinder the hydrocarbons in petrol form peroxy compounds. The accumulated peroxides decompose suddenly and burst into flames producing shock waves. The shock wave hits the walls of the engine and the piston with a rattling sound. This is knocking.

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The reactions that take place in an IC engine are given below (taking ethane as an example for the hydrocarbon present in petrol):

Under ideal conditions C2H6 + 7/2 O2  2 CO2 + 3H2O

Under knocking conditions C2H6 + O2     CH3 –O-O- CH3 (Dimethyl peroxide) CH3CHO + H2O HCHO + CO2 + H2O H2O + CO2

CH3 –O-O- CH3 CH3CHO + 3/2 O2 HCHO + O2   

Note that the overall reaction is the same under both the conditions. One molecule of ethane reacts with 7/2 molecules of oxygen forming carbon dioxide and water with the release of energy. Under ideal conditions, the energy is released at a uniform rate. Under knocking conditions, the energy is released slowly at first followed by a lag (formation of peroxides) and finally the energy is released at a very fast rate (decomposition of peroxides).

Ill effects of knocking 1. Decreases life of engine 2. Causes Piston wrap 3. Consumption of fuel is more Octane Number  The resistance to knocking offered by petrols is expressed in terms of an arbitrary scale called octane number  Octane number is the percentage by volume of isooctane present in a mixture of isooctane and n – heptane which has the same knocking characteristic as the petrol under test. The octane value of isooctane is arbitrarily taken as 100 and that of n – heptane as zero. Different standard mixtures ( 90:10; 80:20, 75:25 etc) of isooctane and n–heptane are prepared and the compression ratio of each of these is determined under standard conditions. The compression ratio of the fuel under test is determined under the same conditions. Page 9

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Notes by Maheshwara Reddy , Dayaynanda Sagar College of Engineering, Bangalore

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Suppose the compression ratio of the fuel is same as that of 80 :20 mixture, the octane number of the fuel is 80.

Cetane Number: The resistance to knocking offered by diesels is expressed in terms of an arbitrary scale called cetane number  It is the percentage by volume of cetane present in a mixture of cetane and methyl naphthalene which has the same knocking characteristic as the diesel under test.  Prevention of Knocking  Addition of lead tetraethyl (TEL) to Petrol: Lead tetraethyl decomposes the peroxides formed and prevents knocking. In the process, lead gets deposited on the inner walls of the engines and at spark plugs. Hence dichloroethane and dibromoethane are added along with tetraethyl lead. These convert the lead into lead halides, which are volatile and escape with exhaust gases.  The release of lead compounds pollutes the atmosphere.  Catalytic converters (rhodium catalyst) are used in IC engines to convert CO in the exhaust to CO2. Lead tetraethyl used as anti knocking agent poisons the catalyst and hence leaded petrol is not advisable in such IC engines.  Addition of MTBE: Methyl tertiary butyl ether (MTBE) is added to petrol (unleaded petrol) to boost its octane number. The oxygen of MTBE brings about complete combustion of petrol preventing peroxide formation and hence knocking is prevented. MTBE can be used as antiknocking agent in IC engines with catalytic converter. Power Alcohol:  This is alcohol-blended petrol.  Gasohol is a blend of 10 – 85% of absolute ethanol and 90 – 15% of petrol by volume and is used as a fuel in the United States. Absolute alcohol is used in the preparation of Power alcohol to prevent phase separation.  Alcohol contains higher percentage of oxygen than MTBE and hence brings about complete oxidation of petrol more effectively.  Therefore power alcohol has better antiknocking characteristics than unleaded petrol. Advantages of power alcohol  power output is high  does not release CO, causes less pollution.  alcohol is obtained from molasses, a agricultural product and hence renewable.
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biodegradable. ------------------------------------

Questions 1. Give the classification of fuels with examples. 2. Explain the process of fluidized bed catalytic cracking of petroleum 3. Calculate the calorific value of coal sample from the following data: Mass of coal: 1g, water equivalent of calorimeter: 2 Kg Specific heat of water: 4.187 KJKg-1C-1 and rise in temperature: 4.8oC 4. Describe how the calorific value of a gaseous fuel is determined using Boy‘s calorimeter. 5. What is meant by cracking? Describe fluidized bed catalytic cracking. 6. On burning 0.83 x 10-3Kg of a solid fuel in a bomb calorimeter, the temperature of 3.5Kg of water increased from 26.5 oC to 29.2 oC. The water equivalent of calorimeter and latent heat of steam are 0.385Kg and 4.2 x 587 KJ/Kg respectively. If the fuel contains 0.7% hydrogen, calculate its gross and net calorific values. 7. What is reforming of petroleum? Give any three reactions involved in reforming. 8. Calculate the gross and net calorific values of a gaseous fuel at STP given 0.03m3 of the gas at STP raised the temperature of 6 Kg of water by 16K and 13.8 cm 3 of water was collected. Specific heat of water is 4.18 KJKg-1C-1 and latent heat of steam at STP is 2.45 KJkg-1 9. What is power alcohol? Give its advantages as a fuel. 10. Define Gross and Net calorific values. Explain Bomb‘s calorimetric method of determining calorific value of a solid fuel. 11. Calculate Gross calorific and Net calorific values of a coal sample from the following data: Weight of coal sample taken: 8.5 x 10-4 Kg Weight of water taken in the calorimeter: 3.5 Kg Water equivalent of calorimeter 0.5 Kg Initial temperature of water 25 oC Final temperature of water 27.5 oC Percentage of H2 in the coal sample 2.5 Latent of Heat of steam 2455 kJ/Kg 12. What is octane number? Explain with equations how reformation of gasoline enhances its octane rating. 13. Calculate Gross calorific value of a coal sample from the following data: Weight of coal sample taken 5.5 x 10-3 Kg Weight of water taken in the calorimeter: 2.5 Kg Water equivalent of calorimeter 0.5 Kg Initial temperature of water 24 oC
Notes by Maheshwara Reddy , Dayaynanda Sagar College of Engineering, Bangalore

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Final temperature of water 28 oC 14. What is knocking? What are its ill effects? Give the mechanism of knocking. How can knocking be prevented?

FUEL CELLS These are galvanic cells in which electrical energy is obtained by the combustion of fuels. Here, the fuels are supplied from outside and do not form integral part of the cell. These do not store energy. Electrical energy can be obtained continuously as long as the fuels are supplied and the products are removed simultaneously. In these aspects fuel cells differ from conventional electrochemical cells Advantages of fuel cells:  Power output is high.  Do not pollute the atmosphere  Electrical energy can be obtained continuously. Hydrogen – oxygen fuel cell
1.23 V
Anode H2 e e Cathode O2 Porous graphite electrode coated with platinum electrocatalyst

Polystyrene sulphonic acid ion exchange membrane in KOH H2 O2 + H2O

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Wicks for maintai ning water It has an anodic compartment and cathodic compartments. balance graphite electrodes impregnated with Pt-Ru-Co. Hydrogen is bubbled through the anodic compartment Oxygen is bubbled through the cathodic compartment. Electrolyte is concentrated KOH solution

Both contain

Notes by Maheshwara Reddy , Dayaynanda Sagar College of Engineering, Bangalore

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Reactions:  At anode  At cathode  

H2 1/2 O2

+ 2OH ⇌ 2H2O + 2e + H2O + 2e ⇌ 2OH

Water is formed as the product, which dilutes the KOH, and hence the electrolyte is kept hot and also the cell is provided with a wick, which helps in maintaining the water balance. Uses: in space vehicles.

Methanol – oxygen fuel cell
Cathode + Anode CO2

O2 Anode Cathode Membrane

H2SO4

Excess O2 and water

CH3OH + H2SO4 electrolyte CO
2

It consists of anodic and cathodic compartments. Both the compartments contain platinum electrode. Methanol containing H2SO4 is passed through anodic compartment. Oxygen is passed through cathodic compartment. Electrolyte consists of sulphuric acid. A membrane is provided which prevents the diffusion of methanol into the cathode. Reactions:  At anode: CH3OH + H2O  CO2 + 6H+ + 6e  At cathode: 3/2O2 + 6H+ + 6e  3H2O Advantages:  Methanol has low carbon content
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 The OH group is easily oxidisable  Methanol is highly soluble in water. Uses: in military applications.

Alkaline fuel cells: These operate at 800C.  At anode: hydrogen  At cathode: oxygen  Electrolyte: alkali

Advantages:  Hydrogen and oxygen are cheap.  Since the electrolyte is an alkali, any type of electrode can be used.  When started at room temperature has low efficiency but on operation gets warmed up and gives optimum efficiency. Phosphoric acid fuel cell  These operate at 2000C.  At anode: hydrogen or pure LPG  At cathode: air  Electrolyte: conc. Phosphoric acid adsorbed on a solid..  Electrodes are made of Teflon. Uses: in supplying light and heat in buildings. Molten carbonate fuel cell  These operate at 6000C.  At anode: hydrogen  At cathode: oxygen  Electrolyte: LiAlO2 + Li2CO3 + K2CO3 Reactions  At anode H2 + CO32  CO2 + H2O + 2e  At cathode 1/2 O2 + CO2 + 2e  CO32  Nickel electrodes with a small amount of Cr are used. Solid polymer electrolyte cell  These operate up to 2000C  Anode: hydrogen  Cathode: oxygen  Electrolyte: ion exchange membrane such as Nafion R  Anode and cathode are made of platinum electrodes.
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Uses: in space vehicles Solid oxide fuel cells  These operate at 10000C  Anode: Ni on ZrO2  Cathode: strontium doped LaMnO2  Electrolyte: ZrO2 – Y2O3 Advantage: does not corrode Uses: In locomotives since large amount of heat is evolved. Biochemical Fuel Cells  These operate at 0 – 400C  These convert chemical energy into electrical energy using bioorganisms.  An example is a biochemical fuel cell which the oxidation of glucose in the presence of FAD as the enzyme and methylene blue (MB) as intermediate. The active material at anode consists of glucose , FAD and MB and the cathode consists of a metal such as Mg. C6H12O6 + FAD  C6H10O6 + FADH2 FADH2 + MB  FAD + MBH2 + MBH2  MB +2H +2e C6H12O6  C6H10O6 + 2H+ +2e Mg 2+ + 2e  Mg at anode at cathode

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Animation for knocking: 1. 2. Under ideal conditions: the inner circle arcs move towards the top with uniform speed. Under knocking conditions: the inner circle arcs move towards the top, stop for a few seconds and then move vigorously so as to hit the walls and the top with force.

Notes by Maheshwara Reddy , Dayaynanda Sagar College of Engineering, Bangalore

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Biotechnology Biotechnology may be defined as application of scientific and engineering principles to the processing of materials by biological agents. Scope and importance of Biotechnology: Biotechnological processes can be used  in brewing, wine making,.  in production of solvents such as acetone, butanol.  in production of glycerol (raw material for production of TNT ,an explosive).  in production of antibiotics such as penicillin , vitamin B12, amino acids  Biotechnology has led to the development of genetic engineering and cloning.  Biotechnology is used in mining, and recovery of metals from their ores.  Biological systems can be used to recognize visual and sensual patterns . hence they are used in biochips for the manufacture of miniature computers. Biotechnological process  Biotechnological processes may be represented by a simple equation Process Substrate + microorganism   Product Engineering

Substrate is the raw material on which the microorganism acts. For e.g., in the preparation of alcohol, molasses is the substrate Microorganism or microbe: it acts on the substrate to give the product. It could be a fungus, a bacteria or an aquatic plant. For e.g., in the preparation of ethanol from molasses, yeast is the microbe and is a fungus. Process engineering involves maintaining conditions such as temperature, pH, aerobic or anaerobic, stirring etc. and also isolation of the product – filtration, distillation etc. Product: it could be a biomass –e.g., ethanol a metabolite – e.g., amino acid a transformed product – e.g., digoxin The process involves Sampling: the sample of air, water or soil containing the microbe is collected. Identification and isolation; the sample is diluted to separate the colonies from one another, identified and isolated by process such as chromatography. Sterilization: it is sterilized using steam or by chemical methods. Bioreactor: it is a vessel which has provisions for monitoring temperature, pH, passing air, charging of the substrate and culture, stirring etc. it is sterilized by passing live steam or by treating with chemicals Page 17

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Substrate: the substrate is taken in the bioreactor and sterilized. Nutrients are added . Culture development; the microorganism is added and the process is allowed to take place under required conditions. Product: the product is isolated by filtration or distillation.

Production of ethanol  Substrate: molasses or starch. o If starch is chosen, it is first hydrolyzed using acid ant then treated with nutrients, which supply N, S, P, minerals and vitamins. o If molasses is chosen as the substrate, it is not necessary to add nutrients because, Molasses contains inositol hexaphosphate (for P), Amino acids – glutamic acid and aspartic acid (for N) Biotin, niacin, pantothenic acid, riboflavin (for vitamins and minerals) Ammonium sulphate is added. It not only supplies S but also maintains a pH of 4.5 Microbe: Sachharomyces cerevesiae isolated from soil (yeast) Temperature: 27 – 30oC. pH 4.5 Condition: anaerobic The reaction is complete in 72 hours. After 72 hours, the concentration of alcohol becomes 12% and the microorganism becomes inactive. In the first 24 hours, the microorganism multiplies. In the next 24 hours the multiplication of microorganism reduces and the production of ethanol increases. In the next 24 hours, the multiplication of microorganism stops and the production of ethanol decreases. The production of ethanol from molasses is called fermentation and follows Emden – Meyerhof – Parnas pathway through formation of pyruvic acid. This is called glycolysis. Glycolysis is defined as production of pyruvic acid from sugar.

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Production of Acetic acid  Substrate: sugar  Microorganism: Acetobacter  Nutrients: K, Na, Mg, Ca, Cu, Co, Mn, Mo, ammonium sulphate, ammonium phosphate, ammonium chloride, iron.  Temperature: 30oC.  pH: 4.5  The conversion of sugar to acetic acid involves 1. Fermentation of sugar to ethanol under anaerobic conditions and 2. Conversion of ethanol to acetic acid under aerobic conditions.
Alcohol Air out Rotating spray

Recycle Wood shavings Air Vinegar To collect

Bioreactor for manufacture of vinegar ( dilute solution of acetic acid)

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The bioreactor is packed with wood shavings and acetobacter is introduced into it. The wood shavings help in immobilization and colonization of the microorganism. Ethanol is allowed to trickle down from the top of the reactor. Air is introduced into the bioreactor maintaining the temperature is maintained at 26 – 30oC. acetic acid collects at the bottom and is separated. Ethanol should not be allowed to oxidize completely as this would damage the microbe.

Production of Lactic acid:      Microorganism: Lactobacillus delbrueckii Temperature: 45oC pH: 4.5 Nutrients: milk, corn steep liquor Lactic acid obtained is treated with CaCO3 to form Ca- lactate. This is purified by crystallization. Dilute sulphuric acid is added to pre calcium lactate when lactic acid is obtained. Page 19

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Production of Acetone       Substrate: starch from potato or maize or rice Microorganism: Clostridium acetobutylicum Temperature: 30oC pH: 4.5 The product is a 1:3:6 mixture of ethanol, acetone and butanol. These are separated by fractionation.

Production of Vitamin B12       Substrate: carbohydrate Microorganism: Streptomyces olivaceus Temperature: 27oC pH: 7 Nutrients: Soya bean, milk, cobalt chloride, dextrose, calcium carbonate. The product obtained is treated with metal cyanide to give cyanocobalamine or VitaminB12

Biosensors:  A biosensor is an analytical device, which consists of a biologically active material which reacts with the analyte producing a change in the properties. This change is recognized, converted into an electrical signal and measured. A biosensor consists of 1. Analyte: the substance whose concentration has to be determined 2. Probe: which is a biologically active material (tissue or enzyme or antibodies); it reacts selectively with the analyte producing a change in the properties. 3. Transducer: which converts the change into an electrical signal 4. Amplifier: amplifies the electrical signal 5. Microprocessor: which processes the signal, interprets and displays the concentration of the analyte.
Analyte

1234

Amplifier

Processor

Display

Biological component

Transducer

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A schematic representation of a biosensor

Advantage of biosensors: 1. selective to the analyte and hence accurate. 2. consume less time 3. respond to even very small amount of the analyte. 4. small size. 5. many substances in the same analyte can be measured by changing only the probe. 6. effective even in viscous and opaque systems. Glucose Biosensor: +
Electrolyte e e Ag/AgCl Saturated KCl Glucose oxidase Membrane (glucose permeable) Glucose (analyte) Teflon membrane (oxygen permeable) Pt electrode

      

The probe used is the enzyme, Glucose oxidase. It is immobilized on polyacrylamide gel. Platinum electrodes surround the gel. Oxygen is passed and the current is measured. The analyte is brought in contact with the biosensor, the glucose in the analyte diffuses through the gel. Glucose is converted to gluconic acid and hydrogen peroxide by the enzyme in the presence of oxygen. Thus concentration of oxygen around the electrode changes. Therefore there is a change in the current which is proportional to the change in the concentration of the oxygen which, in turn, is proportional to the concentration of glucose in the analyte.

Cholesterol biosensor:  The probe used is an enzyme, Cholesterol oxidase.  Here, graphite electrode is used.
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    

The analyte is brought in contact with the probe. The enzyme liberates free cholesterol and oxidizes it to give hydrogen peroxide. Hydrogen peroxide is converted to ferricyanide. The ferricyanide is reduced at the carbon electrode This results in a change in the current which is proportional to the concentration of cholesterol in the analyte.

Ethanol biosensor:  The probe used is alcohol dehydrogenase. The coenzyme is NAD+  pH meter is used.  The analyte is brought in contact with the probe.  The enzyme reacts with ethanol in the presence of co-enzyme liberating H+ ions as shown below C2H5OH + NAD+ + 2e  C2H5O - + NADH NADH  H + + NAD+ + 2e +  The concentration of H ions can be determined using a pH meter.  The concentration of H+ ions is proportional to the concentration of NAD+, which in turn is proportional to the concentration of ethanol . Urea biosensor  Here the probe used is enzyme urease.  Potentiometer is used  The analyte is brought in contact with the probe.  The enzyme acts on urea in the presence of H2O to give NH3 and CO2 NH2CONH2 + H2O  2NH3 + CO2  Membrane electrodes selective to CO2 or NH3 are used  the amount of urea is determined potentiometrically.

Applications of biosensors 1. in medicine: to determine glucose in blood etc. 2. in agriculture: to detect pesticide in fruits vegetables etc. 3. in mining: to detect toxic gases in mines 4. in environmental pollution: to detect pollutants in water, air etc. 5. in defence: to detect toxic gases 6. in food industry: to detect whether food is stale. Release of ammonia or Nitrogen fixation  Nitrogen fixation is the conversion of atmospheric nitrogen to ammonia by organisms. This is of two types: Symbiotic and asymbiotic Symbiotic nitrogen fixation:  In this the microorganism can fix atmospheric nitrogen only in the presence of other organisms.
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 Bacteria, called Rhizobia, infect the root hairs of leguminous plants such as peas beans etc.  The bacteria then multiply within the root hair forming nodules.  The nodules contain nitrogen bacteria and are covered by the cells of the leguminous plants.  The leguminous plant and the rhizobia together synthesize an enzyme called leghaemoglobin, which can take in the nitrogen form the atmosphere and convert it to hydroxylamine and further to ammonia.  A part of the ammonia is taken by the plant and the remaining is released into the soil Asymbiotic nitrogen fixation:  Atmospheric nitrogen is converted to ammonia by some organisms such as Azatobacter independently. This is called Asymbiotic nitrogen fixation.  These organisms produce enzymes which contain carboxyl group.  The Oxygen of the carboxyl group reacts with the nitrogen in the atmosphere and converts it to hydrazine, which is further converted to ammonia. Biofuels 1. Biomass  Plants convert solar energy to biomass and this can be used as fuel. Thus wood is a biomass and has been used as a fuel. Trees such as pine, eucalyptus, aquatic plants like algae and wastes such as manure are biomass. Advantages:  Renewable  High energy content  Less polluting  Cheap 2. Algae Algae are small green plants. These are, dried , powdered and can be used in IC engines. Advantages:  Can be grown in both land and water.  Can be grown even if the soil quality is poor and the water is alkaline.  Does not release CO2 on burning and hence does not contribute to atmospheric pollution.  Energy produced is cheaper 2. Water hyacinth   It is a weed and grows wildly on the surface of water bodies. It is dried, powdered and heated with Klebseills oxytoca in the presence of NaOH. Butanediol is obtained which is distilled and is used to boost the octane number of aviation fuel. Page 23

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4.

Rapeseed oil ( biodiesel)  Rapeseed is crushed and the oil is treated with NaOH and methanol to 50oC.  A mixture of diester and glycerol is obtained.  The diester is separated.  This has properties same as diesel and is called biodiesel. Advantages of biodiesel  Energy output is high  Renewable  Does not cause pollution  No change in the engine design is needed.  Non toxic.

Biophotolysis Breaking of water to hydrogen and oxygen is called photolysis  Algae containing the enzyme alcohol dehydrogenase produce hydrogen form water.  The hydrogen can be used as a fuel. Advantages  High calorific value  Does not cause pollution  The product of combustion is water, which is again used for photolysis.  6. Hydrocarbons Organic wastes contain polymers like carbohydrates, lipids and proteins. These can be broken down by bacteria into amines, acids and alcohols. These are further converted to esters and hydrogen and oxygen. And further converted to hydrocarbons, which can be used as sources of energy.  Thus acetogenic bacteria act on organic wastes and form acetates and H2 and O2. methanogenic bacteria convert the acetates to methane. Methane can be used as afuel. Advantages  Renewable  High energy content  Less polluting Biofertilizers  These are fungi, aquatic plants or bacteria which help in nitrogen fixation and improve the quality of soil to increase crop production. They are a. Symbiotic nitrogen fixers:  Rhizobia in combination with leguminous plants can convert atmospheric  nitrogen into ammonia.
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  

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 Ammonia is released into the soil, converted to ammonium compounds and thus  quality of the soil is improved. b. Asymbiotic nitrogen fixers:  Azatobacter produces enzymes which can form ammonia from atmospheric nitrogen. c. Algal fertilizers:  These are blue green algae which when used in combination with certain cultures such as Anabena, Nostoc are useful as fertilizers for paddy.  Algae are cheap, resistant to pesticides, and can be grown in saline water and poor quality soil. a. Phosphate solubilizers:  These convert insoluble phosphates in the soil into soluble phosphates so that plants can easily absorb them for their growth.  There are certain type of rhizobia which can form complexes with iron in the soil and make iron unavailable to weeds.  Thus weeds are destroyed and the growth of the plant is promoted. b. Mycorrhizae:  These grow with the plant.  They absorb from the soil, substances (that cannot be taken in by the plant directly) and release them to the plant.  In return, they take certain nutrients from the host plant for their own growth. Example, azatobacter. Biosurfactants:  Surfactants have a lyophobic and a lyophilic group in their molecule.  They increase the solubility of organic compounds present in the soil.  They remove non aqueous wastes from the soil.  Rhamnolipids and Trehalose are biosurfactants which are commonly used. They are more advantageous than chemical surfactants because: 1. they are biodegradable 2. they themselves do not add to the contaminants in the soil 3. they are non toxic 4. they can be grown at the site. -------------

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Notes by Maheshwara Reddy , Dayaynanda Sagar College of Engineering, Bangalore

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LIQUID CRYSTALS
DEFINITION: It was observed by an Austrian botanist, Freidrich Reinitzer that solid cholesteryl benzoate on heating becomes a hazy liquid at 145.50C and on further heating turns into a clear, transparent liquid at178.50C. Cholesteryl benzoate is said to exist as a liquid crystal between 145.5oC and 178.5oC. ). On cooling, the change from liquid crystal state to solid took place exactly at the same temperature.
145.5 oC 178.5 oC

Cholesteryl benzoate Solid

liquid crystal state (mesophase)

liquid

 

Thus liquid crystal is a state of matter between highly ordered crystalline and disordered liquid states. In crystalline state, not only do the molecules occupy specific positions but also tend to orient in a preferred direction. Thus the molecules have both positional and orientational order. In crystalline state a compound exhibits anisotropy (different properties in different directions) In liquid state, the molecules neither occupy specific positions nor are oriented in any particular manner. The molecules are free to move at random and collide with one another abruptly changing their positions thus losing both positional and orientational order. In the clear liquid state a compound exhibits isotropy (same properties in different directions) Intermediate between the solid and the liquid state exists the liquid crystal phase, wherein the molecules are free to move but are oriented in a particular manner. The molecules have no positional order but retain some orientational order. In liquid crystal state a compound exhibits isotropy (same properties in different directions)





Solid Liquid

Nematic Liquid crystal

Isotropic Liquid

Temperature



Liquid crystal phase is also called mesophase and the molecules, which can exist in mesophase, are called mesogens.

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

Director : in liquid crystal state the molecules have no positional order but are oriented in a particular direction. The preferred orientation of the molecules of a liquid crystal is called the Director.

Classification of liquid crystals Liquid crystals may be broadly classified into two   Thermotropic liquid crystals: are those that exhibit liquid crystalline state on change of temperature alone. Example: para azoxy anisole. Lyotropic liquid crystals: these exhibit liquid crystalline state in mixtureand when the concentration of one of the constituents is varied. Example: soap.

Requirements for formation of mesophase ( or liquid crystal) The requirements for a substance to form mesophase are 1. it should have elongated structure 2. it should have a central rigid core with flexible ends. 3. it should be polarized or polarizable. Chemical constitution and liquid crystal behaviour: Long chain hydrocarbons have an elongated structure but do not have a rigid core and hence do not form liquid crystals. E.g. n – alkanes cannot form liquid crystals CH3 – CH2 -– CH2 -– CH2 -– CH2 -– CH2 -– CH2 -– CH2 –CH3  Similarly, long chain n- alkanoic acids have elongated structure but do not form liquid crystals. CH3 – CH2 -– CH2 -– CH2 -– CH2 -– CH2 -– CH2 -– CH2 –COOH  If the alkanoic acids form a dimer, they form a cyclic ring at the center due to hydrogen bonding, but the molecule is not rigid enough and hence does not favour mesophase formation. O HO CH3 – CH2 - CH2 - CH2 - CH2 – C C – CH2 - CH2 - CH2 - CH2 - CH3 OH O  If conjugated double bonds are introduced in the above, it gives a rigid core with flexible ends and thus, alkenoic acids can form mesophase O CH3 – CH2 - CH2 - CH = CH – C   HO C – CH = CH - CH2 - CH2 - CH3 OH O Aromatic rings with para substituents have elongated structure with flexible ends can form liquid crystals. Thus a compound with two benzene rings linked through double bonds and substituents at the other ends ( at p and p‘ positions)of the benzene rings can form mesophase. Page 28 

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E.g., para azoxy anisole can exhibit mesophase because It has an elongated structure It has a rigid core comprising of two benzene nuclei linked through N=N It has alkoxy groups at p and p‘ positions as flexible ends.
 The rigid core can be biphenyl, triphenyl, two phenyl rings connected through O double bonds. p- Azoxyanisole The flexible end can be nitro, alkyl, alkoxy, cyano etc CH3O N=N OCH 3

Identification and molecular ordering in liquid crystals:  Liquid crystals exhibit optical anisotropy and hence liquid crystals and their phae transitions can be identified using optical polarizing microscopy.  When thin films of liquid crystals are placed between two glass plates and are viewed through a polarizing microscope, complex patterns, referred to as optical textures, can be observed.  From the texture, it is possible to identify whether the mesophase is nematic, chiral nematic (or cholesteric), smectic, discotic and so on.

Nematic liquid crystals:

   

These have thread like texture. ( Greek nematos = thread). These are formed from optically inactive compounds. The molecules do not have positional order but the molecules are arranged parallel to one another and hence have orientational order. p- azoxy anisole is an example for nematic liquid crystals.

Chiral nematic or twisted nematic or cholesteric liquid crystals.

one pitch- 3600 turn in the director

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    

These are formed from optically active compounds. A group of molecules is oriented at an angle to the adjacent group of molecules such that the director takes a helical path as it travels through the liquid crystal just as a nut is moved on to a screw. The distance through which a director travels as it completes one full rotation is called the pitch of the liquid crystal. Cholesteric liquid crystals exhibit finger print texture. An example for chiral nematic liquid crystal is cholesteryl benzoate.

Smectic liquid crystals:

    

Greek smectos = soap Molecules are arranged in layers. At any instant of time the number of molecules within a layer is much more than the number of molecules between the layers. The time a molecule spends in a layer is much more than the time it spends between the layers. Depending of the orientation of the molecules( inclination to the director) smectic liquid crystals are called smectic A,.B,C etc. They exhibit broken fan like texture.

Discotic liquid crystals:

(a)

(b)

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   

Here the molecules are disk like. These may be columnar liquid crystals or discotic nematic liquid crystals In columnar liquid crystals, the molecules are stacked one above the other forming a column. The columns form definite shape such as hexagon. In discotic nematic liquid crystals the molecules have coin like shape and have no positional order but possess orientational order.

Thus liquid crystals may be classified as follows

Liquid crystals
Calamitic (rod – like) Discotic(disk – like)

Nematic Discotic

Chiral nematic
A B C E F

Smectic

Columnar
nematic

LIQUID CRYSTALLINE BEHAVIOUR IN HOMOLOGOUS SERIES       A series of compounds in which the members have the same functional group and the molecular formulae of adjacent members differ by CH2 is called a homologous series. Thermal stability of the members of a homologous series varies with change in the number of carbon atoms or chain length. Similarly, the thermal stability of a liquid crystal compound may be altered by altering the molecular structure e.g., by increasing its chain length. One of the requirements for liquid crystal formation is that the molecular ordering in the corresponding solid substance should break down in stages on heating In a homologous series, the transition temperatures between crystalline state and mesophase changes with change in the number of carbon atoms in the flexible ends. A similar change is observed in the transtition temperatures between meophase and isotropic liquid state.

PAA, PAAB and MBBA homologous series
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

The structures of (i) para azoxyanisole (PAA) (ii) para alkyl azoxybenzene (PAAB) and para methoxy benzylidene para-n-butylaniline (MBBA) are given below.
CH3O N=N OCH 3  O p- Azoxyanisole (PAA) CH3 N=N CH3  O p-alkylazoxybenzene(PAAB)

CH3O

CH

N

C4H9

p-Methoxybenzylidene-p-n-butylaniline (MBBA)

It may be noted that the difference in the structures of the three molecules is that –  in PAA, the alkyl (CH3) groups are attached to benzene through oxygen atoms  in PAAB the alkyl groups are not linked through oxygen atoms.  in MBBA there is a direct linking of the alkyl chain to the benzene ring on one side (C4H9) and the other alkyl (-CH3) is linked to the benzene ring through oxygen. A plot of transition temperatures against number of carbon atoms for PAA, PAAB and MBBA series is shown in Fig. 1.8.

140 Liquid C 120
0

PAA CH3O N=N  O OCH3

Nematic

Temperature

100 80 Solid 4

Smectic C

Fig.(a)

6 8 10 Number of C atoms Liquid

12
PAAB CH3 N=N  CH3

70 60 C 50 40 30 20 Temperature
0

Smectic A Nematic

Fig.(b) Solid

O

4 5 7 8 9 10 Notes by Maheshwara Reddy6, Dayaynanda Sagar College of Engineering, Bangalore

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Notes by Maheshwara Reddy , Dayaynanda Sagar College of Engineering, Bangalore

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(c)
60
0

MBBA CH3O CH=N C4H9

Liquid

C

Temperature

Nematic

40

Fig.(c) Solid
4 5 8 Number of C atoms 6

20

7

Fig. 1.8. Graphical representation of different phases and transition temperatures of the homologous series

of (a) p-azoxyanisole (PAA) (b) p-alkylazoxybenzene (PAAB) and (c) butylaniline (MBBA)

p-methoxybenzylidine-p-n-

   1.

For each of the series, the upper curve represents the transition from liquid crystal state to liquid state (isotropic) and the lower curve shows the transition from solid state to the liquid crystal state. The region between the two curves gives the range of temperature at which the liquid crystal exists. It can be observed that In general, in all the series, in a curve, as the number of carbon atoms increases, the transition temperature varies and for higher homologues, there is no variation in the transition temperature with change in number of carbon atoms.

2.

In the series where the flexible end is alkoxy chain (PAA), the molecules with even number of carbon atoms, in general, show higher transition temperatures than those having odd carbon atoms. The trend is reversed in the case of PAAB and MBBA

In PAA and PAAB series When the number of C atoms in the flexible end is 1 to 6, the transition is from solid to nematic to isotropic liquid. d. When the number of carbon atoms in the flexible end is 7 or 8, the transition is from solid to smectic to nematic to isotropic liquid e. When the number of carbon atoms in the flexible end is 9 or10, the transition is from solid to smectic to isotropic

3. c.

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4. 5. 6.

The members of MBBA series do not exhibit smectic phase; all the members show transition form solid to nematic to isotropic liquid state. In compounds where the flexible end is alkoxy, the liquid crystalline state is stable at higher temperatures than the ones with alkyl chain as flexible end. It can be seen from the Figure that liquid crystals of PAA are stable between 800 and 1300C whereas those of PAAB and MBBA series are stable at relatively lower temperatures (i.e., between 200 and 60 0C); hence the latter find application in liquid crystal displays (LCDs).    The transition temperatures of the compounds can thus be altered by changing the length of the flexible side chain at the terminal position. Biphenyl and terphenyl systems carrying highly polarizable groups such as nitro and cyano groups also show lower transition temperatures. Such compounds with low transition temperatures have extensive applications in liquid crystal display systems

Electro optic effect: Electric effect:  When a film of liquid crystal is placed between two glass plates, the molecules are oriented in a direction parallel to the surface of the glass.  If an electric field is applied perpendicular to the plate, the molecules of the liquid crystal try to align themselves parallel to the applied field.
Field off Field on

Liquid crystal film kept between two treated glass plates (a)in the field off state(below the threshold value) all molecules and the director orient parallel to the surface (b) in the field on state (above the threshold value) the molecules near the surface orient parallel to the surface whereas in others it is deformed

 

 

When the glass plates are specially treated (such as rubbing with a velvet cloth), the molecules of liquid crystal tend to remain parallel to the plate. When an electric field is applied perpendicular to the surface, the molecules near the surfaces of the glass plates remain parallel to the surface. But the molecules away from the surface, i.e. near the center tend to align themselves parallel to the applied field. This happens at a certain threshold value of the voltage (VTh) applied and increases with increase in the voltage. The liquid crystal is said to be deformed or activated.

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Optical effect.
BRIGHT DARK

4-6 m

3v

Liquid crystal Light Light

 

   

When light passes through two crossed polarisers, light coming out of one polariser is absorbed by the other and hence darkness is observed. However, when a film of liquid crystals placed between specially treated glass plates is placed in between the crossed polarisers and an electric field is applied, the director acts as a wave guide, and light emerges in the orthogonal direction and brightness is observed. Electrooptic effect is utilized in LCDs. The conditions necessary are: Light should be incident either parallel or perpendicular to the glass surface. And The wavelength of the light incident should be  = P  n where P is the pitch of the liquid crystal and n is the difference in the refractive indices perpendicular and parallel to the director.

Thermography.     When light is incident on liquid crystal, a part of it is reflected and a part of it is transmitted. The wavelength of the transmitted light is given by  = P  n where P is the pitch of the liquid crystal and n is the refractive index. If  is in the visible region, the corresponding colour is observed. When the temperature is varied, pitch changes,  and hence the colour changes. This property of the liquid crystal is utilized in thermography.

Applications of liquid crystals in thermography:  In medicine: Tumour cells are at an elevated temperature than normal cells. Liquid crystals show a different colour when in contact with tumour cells than
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    

when in contact with normal cells. Hence liquid crystals can be used to detect subcutaneous tumours. In electronic industry: whenever there is a break in circuit, there will be slight rise in temperature and this can be detected from the variation in the colour of liquid crystal. Liquid crystals can be used in themostrips (to read body temperature) and disposable thermometers. Liquid crystals can be used to detect radiations. Liquid crystals can be used to detect pollutants in atmosphere. Liquid crystal displays are used in watches, calculators, laptop computers, sign boards etc.

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Environmental Chemistry
Industrialization while bringing material benefits and comforts to the mankind, has at the same time brought about deterioration in the environment. Besides increasing the concentration of certain material already present in the atmosphere, it has introduced in it new undesirable constituents. For instance, industrial units and various transport media constantly release into the atmosphere gases such as carbon monoxide, oxides of nitrogen and sulphur, which have a disastrous effect. In addition, natural causes such as earthquakes, volcanic eruptions and storms have also contributed to environmental pollution. The indiscriminate use of biotic and energy components at a a rapid rate has caused further damage to the environment.

Air pollution
Air pollution is the presence of contaminants in atmosphere in quantities such that it is injurious to human, plant animal life and property The main pollutants in the atmosphere are SO2 (sulphur dioxide), CO (carbon monoxide), oxides of nitrogen, particulate matter and lead. Sulphur dioxide: Sources:  Combustion of fossil fuels – coal and crude oil contain up to 3% sulphur.  roasting of ores – sulphide ores on roasting, are converted to sulphur trioxide. This, when let into the atmosphere, combines with the moisture in the atmosphere to form sulphuric acid. for example, roasting of galena , the sulphide ore of lead 2PbS + 3O2  2PbO + 2SO2 2SO2 + O2  2SO3 H2O + SO3  H2SO4  oxidation of l H2S – Hydrogen sulphide is formed during the decay of plants. This, on oxidation releases sulphur dioxide into the atmosphere. 2H2S + 3O2  2H2O + 2 SO2  Volcanic eruptions also emit sulphur dioxide.

Ill effects of SO2:  Sulphur dioxide pollution in the atmosphere affects causes the following damages :  In humans : it causes eye irritation, cough, lung diseases including lung cancer and asthma  In plants: it causes damage of leaves, bleaching of chlorophyll which turns leaves brown, damage to crops and to growth of plants.  Others: Yellowing of paper and wearing away of leather are other ill effects.

Control:
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 

The gases evolved during combustion of fossil fuels are passed through calcium carbonate when SO2 is converted to calcium sulphite. CaCO3 + SO2  CaSO3 + CO2 lime is added to coal and roasted at high temperature so that CaO formed combines with SO2 to form calcium sulphate. CaO + SO2 + ½ O2  CaSO4

Carbon monoxide
Sources:  Oxidation of methane: Methane is formed during decay of vegetable matter. Oxidation of methane releases carbon monoxide into the atmosphere.  Automobile exhaust- carbon monoxide is formed during the combustion of fuel such as petrol and is released into the atmosphere through the exhaust  Incomplete combustion of fossil fuels: coal when undergoes incomplete oxidation, forms carbon monoxide and pollutes the atmosphere. 2C + O2  2CO  Industries: carbon monoxide is released by industries such as iron and steel and petroleum . CO2 + C  2CO 2CO2  2CO + O2

Ill effects:  Haemoglobin in blood can form a complex with oxygen and hence functions as carrier of oxygen.  When the atmosphere is polluted with carbon monoxide, on inhalation, CO combines with the hemoglobin to form carboxy haemoglobin and hence oxygen carrying capacity of the blood decreases.  This causes, headache, dizziness, unconsciousness.  When inhaled for a long duration it may cause even death. Control:  Using catalytic converter in automobiles.

Oxides of nitrogen Nitric oxide, nitrogen dioxide and nitrous oxide are the three main oxides of nitrogen found in the atmosphere
Sources: The sources for the oxides of nitrogen are:  Bacterial decomposition of nitrogenous compounds – bacteria in the soil act on the ammonium compounds present in the soil, convert them to ammonia and finally release oxides of nitrogen into the atmosphere. 4NH3 + 5O2  4NO + 6H2O
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Combustion during lightning – during lightning, oxygen and nitrogen in the atmosphere combine to give oxides of nitrogen. N2 + O2  2NO 2NO + O2  2NO2  Industries and automobile exhaust - Air is sucked into the IC engines. At high temperatures, nitrogen and oxygen in the air combine to form nitric oxide. N2 + O2  2NO Nitric oxide escapes through the exhaust. It gets cooled rapidly and combines with oxygen in the air to give nitrogen dioxide. 2NO + O2  2NO2 Ill effects: Pollution due to oxides of nitrogen affects human and plant life: The oxides of nitrogen combine with moisture in the atmosphere to form nitrous and nitric acid. This leads to increase in the acidity of rain water F ormation of photochemical smog: oxides of nitrogen combine with hydrocarbons present in the atmosphere forming peroxyacyl nitrate. Peoxyacyl nitrate causes injury to plants and in human beings it causes fatigue and infection of the lungs Peroxyacyl nitrate formation leads to smog ( fog + smoke). Smog reduces visibility. Fading of dyes is caused in textiles . Control: Using catalytic converter in automobiles. Catalytic converters use Pt/ Rh catalyst. in the presence of the catalysts, the oxides of nitrogen are converted to nitrogen and oxygen . 2NOx  N2 + x O2



Particulate matter
       Particulate matters are solid or liquid suspensions in air. They are also called aerosols. These comprise of dust particles, ash, smoke, fumes and mist.. Sources: Volcanic eruptions. Soil erosion: wind blows away soil and the dust particles are introduced into the atmosphere. Industrial operations such as crushing of solid materials- solid materials are crushed, ground and powdered in industries. During these operations dust is released into the atmosphere. Burning of coal: The noncombustible matter in coal is left behind as ash during the combustion of coal. Incomplete combustion of compounds containing carbon, processing of coal, cement asbestos: These operations also release dust into the atmosphere.

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

Mist – condensation of vapours, sprays etc lead to dispersion of liquids in the atmosphere thus forming mist.

Ill effects Presence of particulate matter in the atmosphere has the following effects:  Decrease in visibility: Particulate matter interfere inn the transmission of light and hence affect visibility.  Particulate matters enter the lungs causing wheezing, bronchitis, and asthma in human beings.  In plants the particulate matter settle on the leaves blocking the stomata thereby affecting the plant growth. Control: Particulate matter in the atmosphere can be controlled using a. Gravitational settling chambers b. Centrifugal separators c. Fabric filters d. Wet scrubbers e. Electrostatic or Cottrell separators

Charged wire (-ve) Flue gas

Charged plate (+ve) Gas out

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a.

(e) Gravitational settling chambers: figure (a) Here the flue gas is allowed into a rectangular settling tank at a slow rate so that the suspended particles in the gas get deposited. The particles are later removed.

b. Centrifugal separators figure (b) With the help of a cyclone, the gas is led into a chamber tangential to the cross section of the chamber. The gas moves in a spiral manner. Due to the centrifugal forces, the particles in the gas move towards the wall of the chamber and get deposited. c. Fabric filters: figure (c) These consist of bags made of cotton, wool or artificial fibers ceramics. Theses can filter fine particulate matter. Flue gas is passed through a chamber containing a series of such bags. The particles are filtered and clean gas escapes. The particulates collect at the bottom and are removed periodically. d. Wet scrubbers: figure (d) Flue gas is let into a chamber which has two sections – converging section and diverging section. The flue gas enters the converging section and water is sprayed from the top at right angles. The droplets of water take away the particulate matter in the gas. e. Electrostatic or Cottrell separators: figure (e) The flue gas is passed into a chamber containing a series of charged plates. Between the plates wires charged to about 40000 volts are placed. As the flue gas passes through, the particles in it collide with the ionized gas molecules and the particles get charged. The positively charged particles now move towards the wire and get deposited. The negatively charged particles move towards the plates and settle. The gas which is now devoid of particulate matter goes out.

Lead pollutant
Sources:  The exhaust from automobiles which use lead tetraethyl as antiknocking agent when TEL is used as antiknocking agent, lead is converted to halide and released into the atmosphere. This leads to increase in the concentration of lead in the atmosphere.  Paint pigments : Litharge and red lead ( oxides of lead ) and lead chromate are used as pigments. These cause lead pollution  Plumbing systems- lead pipes are used for plumbing and these may cause lead pollution
Notes by Maheshwara Reddy , Dayaynanda Sagar College of Engineering, Bangalore

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Ill effects:  Lead competes with calcium and enters the blood and bone marrow.  The lead interferes in the manufacture of red blood corpuscles and abnormal multiplication of blood cells and thus leads to anaemia and blood cancer in human beings.  Lead enters the blood and various organs of the body including the brain and the Kidneys leading to dysfunction of the kidney and damage to the brain.

Photochemical smog
  Smog is a mixture of smoke and fog. Oxides of nitrogen and hydrocarbons are let into the atmosphere from automobile exhaust. The action of sunlight on these pollutants leads to the formation of peroxyacyl nitrate which causes photochemical smog.

N2 + O2  2NO 2NO + O2  2NO2
NO 2 sunlight NO  O  

O + O2  O3 RCH CHR + O2 (hydrocarbon)
RCH  + O2 2
RCH 2 O  2 RCH 2 O  HO  2

 RCO   RCH  3 2

RCHO
RC
O

 RCH 2 O  2 + NO  NO2 + RCH 2 O  HO   RCHO + O2  2  NO HO   NO 2  + HO   RC O  + H2O NO RCO   RC + O2  3

O

O O NO2 Peroxyacyl nitrate (PAN)

Ozone depletion
Formation of ozone in the atmosphere:  Ozone absorbs uv radiations and is broken into atomic and molecular oxygen.

uv  O2  C  2O O3  O + O2  The products formed combine again to form ozone

Notes by Maheshwara Reddy , Dayaynanda Sagar College of Engineering, Bangalore

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O + O2  O3 and hence a dynamic equilibrium is set up due to which the concentration of ozone in the atmosphere remains constant.  The ozone layer protects the earth from the harmful uv radiations.  If the concentration of ozone is reduced (ozone depletion), the concentration of uv radiations reaching the earth increases.  This leads to irritation of the eyes, skin cancer and damage to immune system in human beings  In agriculture it causes decrease in productivity. Causes of ozone depletion  Chlorofluorocarbons (CFCs) are used as refrigerants, aerosols and as industrial  solvents.  CFCs are noncombustible and volatile. They reach the atmosphere and are  broken down into chlorine free radicals by uv radiations.
  CF2 Cl   C l CF2 Cl2 The chlorine free radical brings about the degradation of ozone
 

uv - C


Cl  O 3



ClO  O 2


ClO  O 

Cl  O 2



Thus CFCs reduce the concentration of ozone in the atmosphere causing ozone hole.

Ill effects  Due to ozone hole, the uv radiation increases causing eye infections, skin cancer in human beings and decrease in photosynthesis in plants.  The temperature on the earth‘s surface is raised and this leads to global warming. Control of ozone depletion:  Ozone depletion can be controlled by using hydrochlorofluorocarbons and hydrofluoroalkanes in place of CFCs. These contain more hydrogen in their molecule and undergo oxidation readily.

Green house effect
     Most of the infrared radiation from the sun is absorbed by the earth‘s surface and a small amount of it is reflected back. An equilibrium is established and this keeps the earth‘s temperature constant. Green house gases such as carbon dioxide, methane, ozone and CFCs absorb the infrared radiations and reemit into the earth. This raises the temperature of earth. This is called green house effect and leads to global warming. Page 45

Notes by Maheshwara Reddy , Dayaynanda Sagar College of Engineering, Bangalore

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Sources:  The main cause for green house effect is carbon dioxide.  The sources of carbon dioxide are combustion of fuels, degradation of vegetable matter, deforestation and industrial activities. Ill effects:  Due to green house effect and global warming, glaciers and icecaps would melt raising the sea level.  The winters would be shorter and summers would be longer.  Weeds , insects and rodents thrive better in warm conditions and these damage the crops. Control:  Use of non fossil fuels as energy sources, using alternatives for CFCs, afforestation are some of the methods for control of green house effect.

Notes by Maheshwara Reddy , Dayaynanda Sagar College of Engineering, Bangalore

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Notes by Pushpa Mohan, NIE, Mysore ENGINEERING CHEMISTRY

ELECTROCHEMICAL ENERGY SYSTEMS
SESSION – 1 Introduction      Electrochemical energy systems involves the study of interconversion of chemical energy to electrical energy and vice versa. A cell consists of two electrodes, each electrode (or metallic conductor) in contact with an electrolyte (or ionic conductor)comprises an electrode compartment. If the electrolytes are different, the electrode compartments may be coupled through a salt bridge. The salt bridge is an agar jelly saturated with potassium chloride or ammonium nitrate, used to connect the electrode compartments. It provides an electrical contact between the two electrodes. Electrochemical cells

Electrolytic cell 1. The cell converts electrical energy into chemical energy. 2. A non-spontaneous reaction is driven by the external source of current. 3. Example: Electrolysis of molten sodium chloride.

Galvanic cell 1. The cell converts chemical energy into electrical energy. 2. Electric current is generated due to spontaneous reaction occurring inside the cell. 3. Example: Daniell cell

Fig:1 At anode: 2Cl-  Cl2 +2eAt Cathode: 2Na++2e- 2Na Net cell reaction: 2Na++2Cl-2Na+Cl2

Fig:2 At anode: Zn  Zn+2 +2eAt Cathode: Cu+2+2e - Cu Net cell reaction: Zn+Cu+2Zn+2 +Cu

Notes by Maheshwara Reddy , Dayaynanda Sagar College of Engineering, Bangalore

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Single Electrode Potential Definition: “The tendency of an electrode to either lose or gain electrons when it is in contact with the solution of its own ions‖.  Single electrode potential is also known as half cell potential.  The electrode potential may be termed as oxidation potential or reduction potential, when oxidation or reduction takes place respectively at the electrode with respect to Standard Hydrogen Electrode (SHE) as a reference electrode. Origin of Electrode Potetnial  When a metal ‗M‘ is in contact with the solution of its own ions M n+ to constitute a half cell, any one of the following possibilities can occur: 1. Metal ion (Mn+) may collide with the metal surface (M) without undergoing any change. 2. Metal atom on the electrode may lose ‗n‘ electrons and changes to Mn+, i.e. oxidation reaction. Fig-3         Metal ion (Mn+) may collide with the electrode and may converted into Metal atom by gaining ‗n‘ electrons, i.e. reduction reaction. If the metal atom has a high tendency to lose electrons (i.e.oxidation), it enters the solution as Mn+ and the released electrons are accumulated on the electrode. This develops negative charge on the electrode. When Mn+ has a greater tendency to gain electrons (i.e. reduction) and changes to metal M at the electrode surface, a positive charge is developed on the electrode. Due to above processes, a state of equilibrium is established between the metal atom ‗M‘ and its ions Mn+. i.e. Mn++ ne-  M.  At equilibrium negative or positive charge developed on the metal, attracts the positively or negatively charged ions respectively present in the solution. Hence an Electrical Double Layer (EDL) is formed at the interface, called Helmoltz Electrical Double Layer. Due to EDL a difference in potential is set up between an electrode and the solution. At equilibrium the potential difference between a metal and the solution remains constant and is known as electrode potential. The electrode potential is given a positive sign or negative sign if the electrode reaction is reduction or oxidation respectively when connected to SHE, the potential of SHE is arbitrarily fixed as zero.

SESSION - 2 Standard Electrode Potential    It is defined as ―the tendency of a metal to lose or to gain electrons when the electrode is in contact with its salt solution of unit concentration at 298K‖. The standard electrode potentials (Eo) of a number of electrodes are determined with respect to SHE and they are arranged in the increasing order of their electrode potential values a series obtained is known as Electrochemical series. (cf. Table-1). Table-1: some standard electrode potentials (Eo) for aqueous solutions

Electrode Eo (volts) Notes by Maheshwara Reddy , Dayaynanda Sagar College of Engineering, Bangalore

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Li/Li+ K/K+ Ca/Ca2+ Na/Na+ Mg/Mg2+ Al/Al3+ Zn/Zn2+ Fe/Fe2+ Pt/H2/ H+ Cu/Cu2+ Ag/Ag+ Pt/ Pt4+ Au/Au+ 

-3.04 -2.92 -2.90 -2.71 -2.40 -1.70 -0.76 -0.44 0.00 +0.34 +0.80 +0.86 +1.50

Important features of the electrochemical series are: 1. Metals at the top of the series are highly reactive and readily lose electrons to give cations where as the metals present at the bottom of the series are less reactive. 2. Difference in the electrode potential values between the two electrodes is large, results higher cell potential.

3. From the value of standard electrode potential for a cell reaction, its equilibrium constant can also be evaluated using the relation : log Keq= nEo/0.0592 Nernst Equation:    From thermodynamics point of view, the electrode in contact with reversible ions constitute the system. Consider a general red-ox reaction: Mn++ ne-  M. ----(1) 

Free energy change for a reversible reaction is given by G = G0 + RT lnQ ----(2)  For a reversible reaction the electrical energy is produced by decreasing the free anergy of the system i.e., G = - nEF and G0= - nE0F ----(3) (where, G= free energy change, G0= standard free energy change, E=electrode potential; E0=standard reduction potential n=number of electrons change; F is Faraday = 96,500C mol-1)  Where ‗Q‘ is the reaction quotient of the concentration of the products and reactants, i.e. Q=

[Products] [M ]  [Reactants] [ M n  ]

----(4)

by substituting Eqs.(3) and (4) in Eq.(2)

[M ] [ M n ] RT [M ] E = E0  ln nF [ M n  ] RT 1 E = E0  ln nF [ M n  ] 2.303 RT E = E0  log M n   nF
-nEF = -nE0F+ RT ln Eq. (8) is called Nernst Equation.

----(5) ----(6) ----(7) (since [M]=1) ----(8)

Notes by Maheshwara Reddy , Dayaynanda Sagar College of Engineering, Bangalore

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(R is a solution constant = 8.314 J K-1 mol-1; T= temperature in absolute scale (K)) E = E0 

0.0591 log M n   n
0

at 298 K

----(9)

The cell potential may be calculated by using the relation Ecell = E cell   

[ M n  ]cathode 2.303 RT ----(10) log nF [ M n  ]anode

The electrode potentials vary with temperature and the concentration of metal ions. The term Electrode Potential (E) refers to the Reduction Potential, also depends upon the nature of the metal.

Cell Representation Galvanic cells are represented with the help of symbols and formulae. The conventions adopted for such cell formulations are: 1. The electrode which is pumping electrons to the outer circuit (anode) is to be written in the LHS and the electrode which receives electrons from the outer circuit (cathode) to be represented in the RHS. 2. The concentration of solutions, pressure of gases and physical state of the solid or liquid involved are indicated by suitable signs within brackets. A vertical line () or a semicolon (;) is used to represent the interfaces across which a potential 3. difference exists.Ex: Zinc rod dipped in Zinc sulphate solution; ZnZnSO4(aq) 4. Anode to be represented as MMn+and cathode in the form Mn+M. 5. The two half cells are connected with the help of a salt bridge is indicated by a double vertical line (). Ex: In Daniell cell (cf. Fig-2) the two electrodes connected by salt bridge, ie., ZnZnSO4(aq)  CuSO4(aq) Cu 6. The potential difference between the two electrodes, called EMF (Electro Motive Force), is stated in volts. Ex: Ecell = Ecathode -Eanode. EMF of a Cell Electro chemical cell consists of two half cells, one of these electrode have relatively higher reduction potential than the other electrode. Hence, the electrons flow from anode (electrode of lower reduction potential) to cathode (electrode of higher reduction potential). The driving force which operates between the two electrodes due to the difference in electrode potentials is EMF of the cell. SESSION-3 Measurement of Single Electrode Potential    Measurement of single electrode potential is not possible, only difference in the potentials between the two electrodes can be measured using potentiometer. By knowing the potential of one of the electrode, the potential of the other can be calculated. To determine the single electrode potential (for ex: Zinc electrode), it is coupled with the reference electrode (SHE) through a salt bridge and the cell may be represented as: ZnZnSO4 HCl (1M); H2(g)(1 atm)Pt.

Notes by Maheshwara Reddy , Dayaynanda Sagar College of Engineering, Bangalore

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 

The emf of the above cell can be measured when no current flows through the circuit. This method is also known as null deflection method. The two electrodes are connected to the potentiometer, balancing lengths are measured for the test cell and the standard cell (ex: cadmium cell, ESC=1.018 V) when galvanometer shows zero deflection. The cell potential is computed using the relation, Ecell=  

 l1  l2

  E SC ; (where l1 and l2 are the balancing lengths obtained from the experiment for  

experimental cell and the standard cell respectively). Fig:4   The single electrode potential is calculated by substituting the potential values in the relation: Ecell = Ecathode -Eanode (or) Ecell = ESHE -EZn,. ( where ESHE =0). The electrode reactions for the above cell are: At anode: Zn  Zn+2 +2eAt Cathode: 2H++2e- H2(g) Net cell reaction : Zn+2H+ H2(g)+Zn+2

Concentration Cell         It is a type of galvanic cell, consists of two identical electrodes in contact with its salt solution of different concentration. The cell potential is due to difference in the concentrations of the metal ions, hence called concentration cell. The electrode with lesser concentration of metal ions behaves as anode and with higher concentration of metal ions acts as cathode. There is no net chemical reaction in the concentration cell. Example: Fig –5 Two silver rods are dipped in silver nitrate solutions of concentrations C1 and C2 respectively, where C1< C2. The cell may be represented as: Ag(s)AgNO3 (C1) AgNO3 (C2) Ag(s). The electrode reactions are: At anode: Ag(s)  Ag+(C1) + eAt Cathode: Ag+(C2) + e- Ag(s) The EMF of the above cell is: Ecell = Ecathode -Eanode



E cell  E Ag 
0

2.303 RT 2.303 RT 0 log Ag  cathode  E Ag  log Ag  anode nF nF E cell  2.303 RT 2.303 RT log( C 2 )  log( C 1 ) nF nF
   
(or)

E cell 
K

C 2.303 RT log  2 C nF  1

E cell 

0.0591  C 2 log  C n  1

  ;  

at 298

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Numerical Problems: 1. 2. Calculate the potential of Ag-Zn cell at 298 K, if the concentration of Ag+ and Zn +2 are 5.2x10-6M and 1.3x10-3M respectively. E0 of the cell at 298K is 1.5V. An electrochemical cell consists of iron electrode dipped in 0.1M FeSO4 and silver electrode in 0.05M AgNO3 . Write the cell representation cell reaction and calculate the emf of the cell at 298K. (The standard reduction potentials of iron and silver are –0.44V and 0.8V respectively). Calculate the potential of Daniell cell at 250 C, given the electrode potentials of Cu and Zn are 0.34V and –0.76V respectively. Write the electrode reactions and Calculate the EMF of the given cell at 298K, Ag(s)AgNO3 (0.018M)  AgNO3 (1.2M)Ag(s). Calculate the voltage of the cell Mg(s)Mg+2 (1M) Cd+2 (7x10-11M) Cd(s), where E0cell=1.97V. Write the half cell and net cell reactions for the cell Cd(s)Cd+2 (0.01M)Cu+2 (0.5M) Cu(s) The standard reduction potentials of Cd and Cu are –0.4V and 0.34V respectively. Calculate the emf of the cell. 7. 8. Calculate the emf of Copper concentration cell at 250 C, where the copper ions ratio in the cell is 10. Calculate the electrode potential at a copper electrode dipped in a 0.1M solution of copper sulphate at 298K, assuming copper sulphate to be completely dissociated. The standard electrode potential of Cu+2 /Cu is 0.34V at 298K.

3. 4. 5. 6.

SESSION- 4 Reference Electrodes  The electrodes of known potential, with reference to which the potential of any other electrode can be measured, are called reference electrodes.  There are two types of reference electrodes, namely 1. Primary reference electrode, Example: Hydrogen gas electrode 2. Secondary reference electrode, Example: Calomel electrode and silver-silver electrode Limitations of Primary Reference Electrode     The electrode cannot be easily setup. The equilibrium between the two processes is not reached quickly. It is difficult to control the pressure of hydrogen gas at 1 atm. The electrode gets poisoned by impurities

Secondary Reference Electrodes For the sake simplicity and to over come the above difficulties, there was a need for the development of secondary reference electrodes. The potentials of these electrodes are known on Notes by Maheshwara Reddy , Dayaynanda Sagar College of Engineering, Bangalore

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the hydrogen scale and are used in place of hydrogen electrode. These electrodes can be easily set up. Calomel electrode Construction : Fig-6    It is a metal-insoluble salt electrode, where metal in contact with its insoluble salt and the solution contains the anion of the salt. Electrode representation: Hg(s)Hg2Cl2 (paste);ClThe potential values depends on the concentration of the solution used in the construction of the electrode: For 0.1N KCl E=0.3335V (called Decinormal calomel electrode) For 1N KCl E=0.2810V (called Normal calomel electrode) For saturated KCl E=0.2422V (called Saturated calomel electrode) The electrode behaves either as anode or as cathode. If the electrode behaves as anode, the electrode reaction is: 2Hg(l)  Hg2+2 +2eHg2+2 +2Cl- Hg2Cl2(s) 2Hg(l) +2Cl- Hg2Cl2(s)+2eIf the electrode behaves as cathode, the electrode reaction is: Hg2Cl2(s)Hg2+2+2ClHg2+2 +2e-2Hg(l) Hg2Cl2(s)+2e- 2Hg(l)+2ClThe electrode potential may be represented by the Nernst equation as E = E 0  0.0591 logCl   at 298K The electrode potential decreases with increase in the concentration of chloride ions.

 



 

Silver-Silver Chloride Electrode      





It is a metal-insoluble salt electrode, where metal (Ag) is in contact with its insoluble salt (AgCl) and the solution contains the anion of the salt, Cl-. Ag is partly converted to AgCl (Ag is made as an anode) by electrolysis in a chloride solution or by dipping the wire in molten silver chloride. Electrode representation: Ag(s)AgCl ;ClThe potential developed is determined by the chloride concentration of the solution, as defined by the Nernst equation. The potential of the electrode is 0.199V vs SHE at 298K when saturated KCl is used. Potassium chloride is the most widely used electrolyte because it does not generally interfere with pH measurements and the mobilities of the potassium and chloride ions are nearly equal. The electrode reaction is: AgCl(s)+e- Ag(s)+ClThe reaction is reversible.

Silver chloride is slightly soluble in strong potassium chloride solutions, so it is recommended that the potassium chloride to be saturated with silver chloride to avoid stripping the silver chloride off the silver wire. Notes by Maheshwara Reddy , Dayaynanda Sagar College of Engineering, Bangalore

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Advantages of Secondary Electrodes  Construction is very simple.  Maintains the constant potential for a long time. SESSION - 5 Ion Selective Electrode  These electrodes consists of a thin membrane in contact with an ionic solution and the electrode respond to only one specific ion.  These electrodes are very sensitive in their response that even in a solution containing small amounts of different types ions, concentration of a particular ionic species in the mixture can be measured.  Example: Glass electrode. Glass Electrode Construction: Fig-7  Glass membrane selectively responses to hydrogen ions.  The glass is quite hygroscopic and takes up a significant amount of water and forms hydrated layers on each side of the membrane.  This electrode works on the principle that when a thin and low resistivity glass membrane is in contact with a solution containing H+ ions, a potential develops between the membrane and the solution.  Potential developed is a linear function of the concentration of hydrogen ions in the solution.  If the concentration of hydrogen ions are different on either side of the glass membrane, the potential develops across the membrane.  When the concentration of H+ on either side of the membrane are same, no potential should be developed. Practically, certain value of potential is developed. This is called assymetric potential (Easy).  At Equilibrium, Na+(glass) + H+(aq)  Na+(aq) + H+(glass)  If the [H+] ions of one of the solution kept constant, the potential developed is proportional to the [H+] ions in the other solution. Advantages  This electrode can be used to determine PH in the range 0-9, with special type of glass even up to 12 can be calculated.  It can be used even in the case of strong oxidising agents.  The equilibrium is reached quickly.  It is simple to operate, hence extensively used in various laboratories. Limitations  The glass membrane though it is very thin, it offers high resistance. Therefore ordinary potentiometers cannot be used, hence it is necessary to use electronic potentiometers.  This electrode cannot be used to determine the PH above 12. Derivation : Eg= E g0 - 0.0591PH   The given glass electrode is dipped in the unknown solution containing hydrogen ions, constitutes a system. The above system may be represented as: Unknown solution (C1)  glass membrane  0.1N HCl; AgCl  Ag

Notes by Maheshwara Reddy , Dayaynanda Sagar College of Engineering, Bangalore

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    

Ag/AgCl electrode is an inner reference electrode. The potential developed between the glass and the solution interface is analogous to junction potential between two solutions containing H+ions. Since the glass is identical at inner and outer solution, boundary potential depends only on the concentration of H+ ions in the solutions. The boundary potential is: Eb=

C 2.303 RT log 1 nF C2

The potential developed on the glass electrode is the sum of boundary potential, potential of the inner reference electrode (EIRE) and asymmetric potential (Easy). Eg = Eb+ EIRE+ Easy (or) Eg =

C 2.303 RT log 1  E IRE  E asy nF C2



For the given glass electrode, C2 (inner reference solution, 0.1MHCl), EIRE and Easy are constants, called E g0 (standard reduction potential of glass electrode).Therefore the above relation becomes; Eg = E g0 + Eg= E g0 (or)

2.303 RT log[ H  ] nF 2.303 RT H P ; (where PH = - log[H+] nF
; at 298K

Eg= E g0 - 0.0591 PH

Detrmination of PH using Glass Electrode   The given glass electrode is dipped in the unknown solution containing hydrogen ions, constitutes a half cell. It is coupled with reference electrode (ex: calomel electrode) through a salt bridge, where calomel electrode forms an outer reference electrode.

Fig-8  The above cell may be represented as: AgAgCl 0.1M HClglass membraneexperimental solution  Sat. KCl Hg2Cl2 (paste)Hg  In the above cell, the glass electrode behaves as anode and calomel electrode as cathode.  The cell potential may be determined using electronic potentiometer.  The E g0 is obtained by repeating the experiment using the solution of known PH.  The PH value of the experimental solution can be calculated by substituting the values of Ecell, Ecalomel and E g0 in the following relation: Ecell = Ecathode -Eanode Ecell = Ecalomel –Eglass Ecell = Ecalomel - E g0 + 0.0591PH

Notes by Maheshwara Reddy , Dayaynanda Sagar College of Engineering, Bangalore

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P =

H

E cell  E calomel  E g0 0.0591

Solutions for problems given in the session 3: 1. Given: T=298K; E0cell = 1.5V. [Ag+] =5.2x10-6M [Zn+2] = 1.3x10-3M w.k.t

0.0591 [ Ag  ] log n [ Zn  2 ] 0.0591 5.2 x10 6 Ecell = 1.5  log 2 1.3 x10  3
Ecell = E cell 
0

Ecell = 1.5-0.0709 Ecell = 1.4291 V. 2. Given: T=298K; E0Fe = -0.44V; E0Ag= 0.8V [Fe+2] =0.1M [Ag+] = 0.05M cell representation: Fe(s) FeSO4(0.1M)  AgNO3(0.05M)  Ag(s) w.k.t. Ecell = Ecathode -Eanode

0.0591 0.0591 0 log Ag    E anode  log Fe  2  n n  0.0591 [ Ag ] 0 0 Ecell = E cathode  E anode  log Fe  2  n 0.0591 [0.05] Ecell = 0.8-(-0.44)+ log 0.1 2
0 Ecell = E cathode 

3.

4.

Ecell = 1.24-0.0089 Ecell = 1.2311 V. Given: E0Zn = -0.76V; E0Cu= 0.34V w.k.t Ecell = Ecathode -Eanode Ecell = 0.34-(-0.76) Ecell = 1.1 V. At anode: Ag(s)  Ag+ +eAt Cathode: Ag++e- Ag(s) w.k.t

E cell 
E cell

     1.2   0.0591 log    0.018 

0.0591  C 2 log  C n  1

at 298K (n=1)

Ecell = 0.1078 V. 5. Given:E0cell = 1.97V [Mg+2] =1M [Cd+2] = 7x10-11M Ecell = E cell 
0

0.0591 [Cd 2 ] log n [ Mg  2 ]
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Notes by Maheshwara Reddy , Dayaynanda Sagar College of Engineering, Bangalore

[Type text]

Ecell =1.97+

0.0591 log 7x10-11 2

Ecell =1.97-0.3001 Ecell =1.6699 V. 6. Given: E0Cd = -0.4V; E0Cu= 0.34V; [Cd+2] =0.01M; [Cu+2] = 0.5M At anode: Cd  Cd+2 +2eAt Cathode: Cu+2+2e- Cu Net cell reaction : Cd+Cu+2 Cu+Cd+2

0.0591 [Cu 2  ] log Cd  2  n 0.0591 0.5 Ecell =0.34-(-0.4)+ log 2 0.01
0 0 Ecell = E cathode  E anode 

Ecell =0.74+0.0502 Ecell =0.7902 V. 7. Given:

[Cu 2 ]cathode C 2   10 [Cu  2 ]anode C 1
E cell  0.0591  C 2 log  C n  1   ;  
at 298 K

w.k.t

E cell 
8.

0.0591 log( 10) 2

Ecell = 0.0296 V. Given: T=298K; E0Cu= 0.34V [Cu+2] =0.1M

E Cu  2 E Cu  2
E Cu  2 E Cu  2
Questions:

 E0 
Cu

Cu

0.0591 log Cu 2  n 0.0591  0.34  log( 0.1) 2  0.34  0.0296
 0.3105 V.

at 298 K

Cu

Cu

1. What is single electrode potential? Derive the Nernst equation for single electrode potetnial. 2. Discuss the origin of electrode potential. 3. What are concentration cells? Deduce the expression for the EMF of a copper concentration cell. 4. Explain the construction of Ag/AgCl electrode. Give the half cell reaction. 5. Write a note on Calomel electrode. 6. What is an ion selective electrode? Explain its principle and working. Notes by Maheshwara Reddy , Dayaynanda Sagar College of Engineering, Bangalore

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7. Write a note on glass electrode. 8. Explain how glass electrode can be used in the determination of a PH of a solution.

References: 1. Elements of Physical chemistry by S.Glasstone and Lewis. 2. Principles of Physical chemistry by B.R. Puri, L.R. Sharma and M.S. Pathania. 3. Engineering chemistry by Jain and Jain. 4. Text book of Physical Chemistry by P.L. Soni and O.P. Dharmatha. Animation Instruction for Fig3:       Metal atom and the metal ion (Mn+) must be represented by a spherical shape. Size of the metal atom must be slightly bigger than the metal ion. In all the three figs, the metal strip (M) is dipped in the solution containing its metal ions. Represent metal strip and the solution by different colours. In fig3(a), show the metal ion from the solution strikes the metal surface and returns to the solution with out any chemical reaction. In fig3 (b), show metal atom from the metal strip comes to the interface as metal ion and electrons are left on the metal strip. Repeat the above and show the accumulation of charges as shown in the fig3(b) represent two different charges by two different colours. In fig3 (c), metal ion from solution enters the metal lattice (represent the same by positive sign). The negative ions in the are attracted by the positive charge on the metal and repeat the process and show the collection of charges at the interface. finally two layers of charges are accumulated at the interface and they are at equillibrium, called double layer, hence the potential exists.



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BATTERY TECHNOLOGY
Session-1 Introduction  A battery is a portable energy source with three basic components-an anode (the negative part), a cathode (the positive part), and an electrolyte. As current is drawn from the battery, electrons start to flow from the anode through the electrolyte, to the cathode.  It is a device which enables the energy liberated in a chemical reaction to be converted directly into electricity.  The term battery originally implied a group of cells in a series or parallel arrangement, but now it is either a single cell or group of cells.  Examples: It ranges from small button cells used in electric watches to the lead acid batteries used for starting, lighting and ignition in vehicles with internal combustion engines.  The batteries are of great importance based on the ability of some electrochemical systems to store electrical energy supplied by the external source. Such batteries may be used for emergency power supplies, for driving electric vehicles, etc.  For the commercial exploitation, it is important that a battery should provide a higher energy, power density along with long shelf life, low cost and compatible rechargeable units. Battery Characteristics A cell may be characterised in terms of (i) its available capacity (ii) its available energy, and (iii) the power it can deliver. Capacity      It is defined as the quantity of electrical charge measured in Ampere hour (Ah), capable of being provided by a battery during discharge. (One Ah = current of one Ampere flowing for one hour). The theoretical capacity may be calculated using the relation, QT = x (nF), where x (x = w/M) is the theoretical number of moles of the electroactive material associated with the complete discharge of the cell. The practical capacity (Qp) is the actual number of coulombs (or Ah) of electrical charge delivered, it is always lower than the theoretical capacity. Coulombic Efficiency is defined as the ratio of practical capacity to the theoretical capacity. Electricity storage capacity is usually expressed with an Ampere-hour (Ah) rating, which means the amount of electrical current that the battery will deliver over a given number of hours at its normal voltage and at a temperature of 25 OC. For example: A Page 59

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battery rated at 60 Ah, should produce 3 amperes for 20 hours (Example: 60 Ah/3A = 20 hrs, based on a 20 hour discharge). Obviously, higher the Ah rating, the better the battery.
Voltage

 

A measure of the force or "push" given by the electrons in an electrical circuit. It may also be defined as a measure of electrical potential. One volt produces one amp of current when acting against a resistance of one ohm. Voltage of a battery may be calculated using the Nernst equation (cf. Electrochemical energy systems).

Session-2 Current  An electric current, which is a flow of charge, occurs when there is a potential difference.  For a current to flow it requires a complete circuit.  Current (I) is measured in amperes (A), and is the amount of charge flowing per second. (current : I = q / t, with units of A = C s-1) Energy  Energy is defined as the capacity to do work. It is expressed in terms of Joules or calories.  The theoretical energy for one mole of the reaction may be calculated using -G = nFEcell and practical energy is the actual amount of energy delivered for one mole of the reaction.  Energy efficiency is defined as the ratio of useful energy out put to the total energy input.  Energy density* is a measure of how much energy can be extracted from a battery per unit weight or volume of a battery. It is the parameter used to assess the relative cell performance. It is expressed in W/kg. Power



For example, if a battery to be used to operate a toy car, the energy stored in the battery is

transformed into mechanical energy which exerts a force on the mechanism that turns the wheels and makes the car to move. This continues until the stored energy (i.e. charge) is used up completely. In its uncharged condition the battery no longer has the capacity to do work.
*

The energy density is analogous to the size of the fuel tank and the power density is analogous to the octane number of the fuel.

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   

The level of discharge current drawn from a cell is determined principally by the external load resistance. The power (P) delivered is given by the product of the current flowing and the associated cell voltage, is expressed in Watts (W). As more and more current is drawn from a cell, the power initially rises, it reaches a maximum and then drops as the cell voltage falls due to polarisation effects. Power density* is a measure of how much power can be extracted from a battery per unit of battery weight and is expressed in W/Kg.

Cycle life  Cycle is a single charge and discharge of a rechargeable battery, and the number of cycles a battery provides before it is to be discarded is called a cycle life. If the capacity of a battery falls below 60% to 80%, it should be discarded. Shelf life  The period of time a battery can be stored without significant deterioration.
 Aging is subject to storage temperature and state of charge. While primary batteries have a shelf life up to 10 years, lithium- based batteries are good for 2 to 3 years, nickel – based batteries are good for 5 years, etc.

Classification of Batteries: Batteries are classified as primary (non-rechargeable), secondary (rechargeble) and reserve (inactive until activated):

Primary batteries

Secondary batteries

Reserve batteries

A primary battery is one whose useful life is ended when its reactants have been consumed by the

A secondary battery Reserve batteries are special purpose primary can be recharged after discharge under specified conditions. batteries designed for emergency use and also for long term storage. The electrolyte is usually stored separately from the electrodes which remain in a dry inactive state. The battery is only activated when it is needed

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process of discharge. It is non-rechargeable. Primary batteries are often relatively inexpensive; they are used in long-term operation with minimal current drain. Example: Dry cell. Classical Batteries: Zn-MnO2 battery:  Construction:

It behaves as an by introducing the electrolyte into the active part electrochemical energy storage unit. of the cell. Hence deterioration of the active materials

The energy derived during storage can be avoided and also from the external eliminates the loss of capacity due to self current is stored as discharge until the battery is put into use. chemical energy. Example: Lead acid battery. Example: Magnesium-water activated batteries, zinc-silver oxide batteries, etc.

Fig-1 Cathode cap

zinc chloride and ammonium chloride paste paste of MnO2 and graphite powder Graphite rod (cathode) outer cover Zn container (anode)

Session -3
 The Zn-MnO2 battery consisting of a zinc container as anode, and graphite rod as cathode. The electrodes are separated by the electrolyte mixture i.e., graphitised manganese dioxide and a paste of ammonium chloride and zinc chloride in aqueous medium. The MnO2 is mixed with graphite powder to increase the conductivity. The cell representation is: ZnZnCl2(aq),NH4Cl(aq)MnO2(s) C(s) The electrode reactions are: At anode: ZnZn+2 + 2e-

  

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At cathode:

 

Mn2O3+2OHNet cell reaction: Zn + MnO2 + H2OMn2O3 +Zn+2 + 2OHCertain chemical reactions are not directly involved in the electrode reactions and hence do not contribute to the cell potential. These reactions are called secondary reactions. The secondary reactions involved in the Zn-MnO2 cell are: 2NH4Cl +2OH-2NH3+2Cl-+ 2H2O Zn+2 +2NH3+2Cl-[Zn(NH3)2]Cl2 The above secondary reactions are irreversible and hence the cell cannot be recharged. The potential of the dry cell is 1.5V. Applications: Used in portable electronic devices, viz. radios, transistors, tape recorders, flash lights etc. where only small amount of current is required. Advantages: Limitations: When current is drawn rapidly from the cell, the products are build up on the electrodes and results the drop in the cell voltage, the cell capacity is low, the acidic medium in the cell decreases the shelf life.

MnO2 + H2O+ 2e-

    

Lead-acid battery  Construction: Lead-acid battery consist of (in the charged state) electrodes viz. lead metal (Pb) and lead dioxide (PbO2) in the form of plates behaves as anode and cathode respectively (or) the electrodes may be lead grids containing spongy lead in one of the grid (as anode) and the other containing lead dioxide (as cathode). The electrode pairs with inert porous partitions are dipped in an electrolyte of about 37 % H2SO4. In the discharged state both electrodes turn into lead sulfate and the electrolyte is consumed during the process.  The chemical reactions are (charged to discharged): Anode: PbPb+2 + 2ePb+2 +SO4-2PbSO4 Pb + SO4-2PbSO4+ 2eCathode: PbO2+4H++ 2e- Pb+2 +2H2O Pb+2 +SO4-2PbSO4 PbO2+ 4H++ SO4-2 +2e- PbSO4+2H2O The net cell reaction is: Pb + PbO2+ 2H2SO4 2PbSO4+2H2O 2.303 RT 0 The potential of the cell is given by: Ecell = E cell  log[ H 2 SO4 ]2 nF From the above equation, it is evident that the potential of the lead acid battery depends on the concentration of the electrolyte at the given temperature. During charging the above cell reaction is reversed and sulphuric acid is regenerated. 2PbSO4+2H2O Pb + PbO2+ 2H2SO4 Page 63

 

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 The OCV is 2.1V.
 Applications The lead acid battery is preferred for hospital equipment, telephone exchangers, emergency lighting and UPS systems. It is also used in automobiles to start the engine. Advantages 1. Economical for larger power applications where weight is of little concern. 2. Inexpensive in terms of cost, Low maintenance and simple to manufacture. 3. The self-discharge rate is lowest among the rechargeable battery systems. Limitations
1. The lead acid battery has the lowest energy density, making it unsuitable for handheld devices that demand compact size.





2. The performance of the battery at low temperatures is poor. 3. The electrolyte is extremely corrosive nature. 4. Overcharging with excessive charging voltages will generate oxygen and hydrogen gases, may lead to explosion.

5. Low energy density.
6. The electrolyte and the lead content can cause environmental damage (environmental concerns regarding spillage in case of an accident). Session-4 Nickel-Cadmium Battery Rechargeable nickel-cadmium battery is a type of alkaline storage battery, which is classified as a secondary battery. In this cell the electrodes containing the active materials undergo changes in the oxidation state.  Construction: The Nickel-cadmium battery consists of nickel oxyhydroxide (NiOOH) as the charged active material in the positive plate(cathode), together with up to 5% of Co(OH)2, Ba(OH)2 to improve the cell capacity and cycle life, 20% of graphite to increase the electronic conductivity. Cadmium metal (Cd) is the charged active material in the negative plate (anode), along with upto 25% of iron and small quantities of nickel and graphite to prevent agglomeration.  During discharge, the charged nickel oxyhydroxide goes to a lower valence state, i.e. Ni(OH)2, by accepting electrons from the external circuit. The cadmium metal is oxidized to cadmium ions and releases electrons to the external circuit.  The electrodes are isolated from each other by a porous separator, usually non-woven fabric or nylon or polypropylene. This separator material in addition to isolating the plates, contains the aqueous solution of potassium hydroxide with one to two percent of lithium hydroxide as an electrolyte through which the chemical reaction take place.  During recharging of the battery, the reactions are reversed, thus returning the cell to the original voltage and capacity.


The lithium hydroxide is usually added to minimise the coagulation of the NiO(OH) and to prolong the service life by making the cell more resistant to electrical abuse. For low temperature applications, more concentrated KOH solutions are used (without LiOH, which increases electrolyte resistance).

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

The chemical reaction which occurs in a Nickel Cadmium battery is: At anode: Cd  Cd+2+2eCd+2 + 2OH- Cd(OH)2 At cathode: 2NiO(OH) + 2H2O + 2e-2Ni(OH)2 + 2OHThe net cell reaction is: 2 NiO(OH) + Cd + 2 H2O  2 Ni(OH)2 + Cd(OH)2  The above reaction goes from left to right when the battery is being discharged and from right to left when it is being recharged. The alkaline electrolyte (commonly KOH) is not consumed in this reaction.  The open circuit voltage is 1.35V  Uses
These cells are used in military and aerospace applications

These cells are used in electric shavers, transmitters, receivers, photoflash units, etc.  Advantages Possess good load performance and allows recharging even at low temperatures. Long shelf life, simple for storage and transportation. Good low temperature performance. It is the lowest cost battery in terms of cost per cycle. Available in a wide range of sizes, high number of charge/discharge cycles.  Limitations Relatively low energy density, low capacity when compared to other rechargeable systems. It is environmentally unfriendly, since the Ni-Cd cell contains toxic metals. Has relatively high self-discharge and need to be recharged after storage. Modern Batteries Zinc-air battery In metal/air batteries, the reactive anode and air electrode as an inexhaustible cathode reactant. The zinc-air, electrochemical system can be more formally defined as zinc/potassium hydroxide/oxygen, but commonly known as ―zinc-air‖ cell. It ―breathes‖ oxygen from the air for use as the cathode reactant. The limitless supply of air enables the zinc-air cell to offer many advantages compared to other batteries. Zinc-air delivers the highest energy density of any commercially available battery system, and at a low operating cost.  Construction: It consists of nickel plated steel cans. The anode can contains the mixture of zinc powder-electrolyte mix with a gelling agent. The oxygen reduction cathode contains multiple air holes punched at the bottom to provide air access to the cathode. The cathode material is laminated with a Teflon layer on one side and a porous separating membrane on the other. The separating membrane is placed directly over the holes to ensure uniform air distribution across the air electrode. The Teflon layer allows oxygen, to diffuse into and out of the cell, and also provides resistance to leakage. The separator acts as an ion conductor between the electrodes and as an insulator to prevent internal short-circuiting. Page 65

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

 

The alkaline electrolyte employed is an aqueous solution of potassium hydroxide with a small amount of zinc oxide to prevent self-discharge of the anode. Potassium hydroxide provides good ionic conductance between the anode and cathode to permit efficient discharge of the cell. The nominal open circuit voltage for a zinc air cell is 1.4 Volts. The operating voltage is between 1.25 and 1V. Electrode reactions are: At anode: ZnZn+2+2eZn+2+2OH-Zn(OH)2 Zn(OH)2ZnO+H2O At cathode: ½ O2 +H2O+2e-2OH-

Net cell reaction


Zn + ½ O2ZnO





Advantages  Very high capacity for its size.  Constant voltage output for most of their life.  It can be used in medium current applications.  Environmentally safe.  High energy density and low operating cost. Disadvantages  It can be used only if the battery compartment is vented to the atmosphere.  The cells are hygroscopic.  Actual performance of the cell depends on the relative humidity.  They can not be used in watches, as they require atmospheric oxygen to function, and they may emit water which is corrosive to metal parts. Uses  Used in hearing aids.  They are also well suited for use in telecommunication devices such as pagers and wireless headsets.  Zinc-air batteries are often used to power a number of medical devices, such as patient monitors and recorders, nerve and muscle stimulators, and drug infusion pumps.

Session-5 Nickel-metal hydride battery (Ni-MH) Nickel metal hydride (metal hydride is a binary compound formed by the union of hydrogen and other elements) batteries are similar to Ni-Cd battery, but are less toxic and offer higher capacities. Ni-MH batteries have a high self-discharge rate and are relatively expensive to purchase. Construction:  In a Ni-MH cell, a hydrogen storage metal alloy behaves as anode and nickel oxy hydroxide cathode.  At cathode (a highly porous substrate) nickel oxy hydroxide is imprignated.
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 

The electrolyte is an aqueous potassium hydroxide solution. Synthetic non woven material is used as a separator which separates the two electrodes and also behaves as a medium for absorbing the electrolyte.  Electrode reactions are: At anode: MH + OH-—> M + H2O + eAt cathode: NiO(OH) + H2O + e- —> Ni(OH)2 + OHOver all reaction: NiO(OH) + MH —> Ni(OH)2 + M  The open circuit voltage is 1.35V.  During recharging of the battery the above cell reaction is reversed. uses: Ni-MH battery is used in cellular phones, emergency backup lighting, power tools, laptops, portable, electric vehicles.

Advantages and limitations
High capacity, Long shelf life, no maintenance is required, rapid recharge capability, no environmental problems. Its performance is poor. LiMnO2 battery Construction:  Lithium Manganese Dioxide cell, is a primary battery.  Anode is Lithium metal (in the form of disc) and cathode is manganese dioxide (in the form of a pellet).  The electrolyte is lithium halide dissolved in organic solvent  Separator is polypropylene impregnated with the electrolyte. It provides an electrical contact between the two electrodes.  The operating temperature is -40º C to 60º C. Electrode reactions are: At anode: LiLi+ + eAt cathode: MnO2 +Li+ + e-LiMnO2 Net cell reaction: Li + MnO2 LiMnO2 Uses Outdoor use (requiring a low temperature range) and for high-discharge devices, which include digital cameras, portable power tools, heavy-use flashlights, walkie-talkies, portable televisions, handheld video games, etc. Advantages     Highest energy and power densities Higher and stable operating voltage (3.6V / 3.9V) Wider operating temperature range (-400 C to + 850 C) Outstanding storage capability (up to 10 Years) Page 67

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  

Ultimate safety Lowest self discharge (less than 1.5% per year) good discharge performance.

Limitations  Aqueous electrolytes cannot be used in Lithium batteries, because of high reactivity of Li with water.

Reference: Modern batteries: An Introduction to electrochemical power sources; By Colin A. Vincent with Franco Bonino, Mario Lazzari and Bruno Scrosati. Questions: Distinguish between primary and secondary cells. Explain the cell characteristics. Explain the construction, working and applications of a Dry cell. Write a note on Ni-MH battery. Explain the construction and working of a lead acid battery. Write the discharging and charging reactions in lead acid battery. 7. What are secondary reactions? Write the secondary reactions involved in Zincmanganese dioxide battery. 8. Write a note on: nickel cadmium battery and Lithium manganese dioxide battery. 9. Explain the construction and working of a zinc-air battery.
1. 2. 3. 4. 5. 6.

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CORROSION SCIENCE
Session-1 Introduction The term corrosion is used to denote a change. A metal changes from its elementary state to the combined state, more or less rapidly, when it comes into contact with the gaseous/liquid medium. This is actually owing to the chemical interaction between the metal and the environment. Definition Corrosion* is defined as ―all the processes whereby a metal or alloy used as a material of construction is transformed from metallic to the combined state due to interaction with the environment through chemical or electrochemical attack‖ (or) ―The spontaneous destruction and consequent loss of a metal/alloy due to unavoidable chemical/electrochemical attack by the environment‖ Example: 1. When Cu is exposed to the industrial environment it forms an adherent protective green deposit which isolates the metal from the environment, hence the further action is very slow. 2. When iron metal is exposed to the industrial environment, the metal forms a loosely adherent product of hydrated ferric oxide called rust, which is relatively nonprotective. Hence, the fundamental approach to the phenomena of corrosion, the structural features of the metal, reactions which occur at the interface and nature of the environment are to be considered. Electrochemical theory of corrosion  Most of the corrosion cases are electrochemical in nature, taking place by an electrochemical attack on the metal in the presence of moisture/conducting mediumcalled wet corrosion.  According to the theory, when a metal is in contact with the conducting medium or when dissimilar metals/alloys are either immersed partially/completely in a solution, the separate existence of anodic and cathodic area on the metal, results corrosion.  In this corrosion, oxidation of the metal and reduction of species present in solution takes place at anodic and cathodic parts, respectively.  The electrons are transferred through the metal from anode to cathode.  The anodic part of the metal suffers from corrosion and cathode is protected from corrosion.  The rate of corrosion depends on the nature of the product. If the product is soluble/volatile/ unstable, the metal suffers from severe corrosion, if the product is insoluble and stable, prevents the metal from further corrosion.
* *

Definition of corrosion in the context of corrosion science: the reaction of a solid with its environment. Definition of corrosion in the context of corrosion engineering: the reaction of an engineering constructional material with its environment with a consequent deterioration in its properties.

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

Corrosion reactions are: At anode (oxidation reaction): M →Mn+ + neThe reaction at cathode (reduction reaction) depends on the nature of the environment: If the medium is acidic, (a) In the presence of dissolved oxygen : 2H+ + ½O2 + 2e-→H2O (b) In the absence of dissolved oxygen: 2H+ + 2e-→ H2 If the medium is alkaline/neutral, (a) In the presence of dissolved oxygen : H2O+½ O2 + 2e-→2 OH  (b) In the absence of dissolved oxygen : 2H2O+2e-→2 OH  + H2 Example: Rusting of an Iron in the presence of moist air At anode: Fe→Fe+2 + 2eAt cathode: H2O+½ O2 + 2e-→2 OH  Net reaction: Fe+2 +2 OH  →Fe(OH)2 In the presence of excess of oxygen: 2Fe(OH)2+ ½ O2→Fe2O3.2H2O
(rust)

In the limited supply of oxygen: Session-2

3Fe(OH)2+½ O2→Fe3O4.3H2O
(black rust)

Factors affecting the rate of corrosion

Primary Factors (Related to metal) Environment) Factors are:1. 2. 3. 4.    Nature of the metal Physical state of the metal Hydrogen over voltage Nature of the protective layer

Secondary factors (Related

to

1. pH of the medium 2. Temperature 3. Area effect 4. Polarisation

Nature of the metal The position of the metal/alloy in the galvanic series decides the rate and extent of corrosion. The metals with lower electrode potential values are more reactive and more susceptible for corrosion than the metals with higher electrode potential values. The rate of corrosion depends upon the difference in the position of the metals in the galvanic series. Greater the difference, faster is the corrosion at anode. The rate of corrosion is influenced by the physical state of the metal such as, grain size, stress, etc. The smaller the grain size, it is easily soluble and greater the rate of corrosion and vice versa. The areas under stress, tend to be anodic and susceptible for corrosion.

Physical state of the metal   

Hydrogen overvoltage
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

A metal with low hydrogen over voltage (OV) is more susceptible to corrosion, when the cathodic reaction involves hydrogen evolution.  The reduction in the over voltage of the corroding metal/alloy, accelerates the corrosion rate.  Example: when Zn metal in contact with 1N H2SO4, it undergoes corrosion by the evolution of hydrogen gas. The rate of the reaction is very slow, because its O.V. is high (~0.7V). If a few drops of Cu solution is added the rate of corrosion increases since, Cu gets deposited on Zn forming minute cathodes, where the hydrogen OV value is only 0.33V. Nature of the protective layer     In aerated atmosphere almost all metals get covered with a thin surface film of metal oxide. The thickness of the oxide layer varies with respect to the nature of the metal and the environment. The ratio of the volumes of the metal oxide to the metal is called specific volume ratio. If the specific volume ratio is higher, the oxide film is nonporous, protective in nature, prevents the further corrosion and vice-versa. Acidic media are generally more corrosive than alkaline/neutral media. The pH of the solutions decides the type of cathodic reaction. The corrosion of iron in oxygen free water is slow, until the pH<5, the corresponding corrosion rate is much higher in presence of oxygen. The metals which are amphoteric in nature viz. Al, Zn, etc., dissolve in alkaline solutions as complex ions. Corrosion of metals readily attacked by acid can be reduced by increasing the pH of the environment. Example: Zn suffers from severe corrosion even in the presence of mild acidic medium, whereas corrosion is minimum at pH=11. The velocity of a chemical reaction increases with increase in temperature. If the medium is acidic, hydrogen evolution takes place at cathode. The rate of diffusion of H+ towards cathode increases with increase in temperature and enhances the rate of corrosion. If the medium is alkaline / neutral, oxygen absorption takes place at cathode. Since the solubilities of the dissolved gases decreases with increase in temperature, the rate of corrosion also decreases. Passive metals becomes active at high temperature and increases the rate of corrosion with increasing temperature. Ex. Caustic embrittlement in high pressure boilers. The rate of corrosion (x) is directly proportional to the ratio of area of cathode to the area of anode. i.e., x = area of cathode/ area of anode Page 71

pH of the medium    

Temperature:    

Area effect 

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 

Higher the value of x, greater is the rate of corrosion.. When anode is small and cathode is large all the electrons liberated at anode, are consumed at the cathodic region. Therefore, the rate of anodic reaction is greater and increases the extent of corrosion. The anodic and cathodic reactions takes place simultaneously during corrosion, and causes polarization of the electrodes. The polarization of anode or cathode decreases the corrosion rate substantially. The presence of depolarizers reduces the polarization effect and thereby increases the rate of corrosion. The addition of complexing agents around anode and/or the presence of oxidizing agents around cathode, acts as depolarizers.

Polarisation    

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Session-3 Types of corrosion

Differential metal corrosion corrosion Ex: Galvanic corrosion embrittlement Differential metal corrosion 

Differential aeration corrosion Ex: Pitting corrosion Waterline corrosion

Stress

Ex:

caustic

    

When two dissimilar metals are in direct contact with one another and exposed to a corrosive conducting medium, the metal higher up in the electrochemical series behaves as anode and suffers from corrosion, whereas the metal lower in the electrochemical series becomes cathode and protected from corrosion. This type of corrosion is also known as Galvanic corrosion. If the potential difference between the electrodes is high, greater the extent of corrosion. Oxidation /reduction takes place at anode/cathode respectively. The reduction at cathode depends on the nature of the corrosive environment. In acidic medium, corrosion occurs by hydrogen evolution; while in alkaline/neutral solution, oxygen absorption takes place. When Zn and Cu metals are electrically connected and exposed to an electrolyte, Zn (higher in electrochemical series) forms anode and suffers from corrosion whereas Cu (lower in electrochemical series) forms cathode and protected from corrosion. Examples: Steel screws in a brass marine hardware Steel pipe connected to copper plumbing This type of corrosion is due to the formation of differential aeration cell or oxygen concentration cell. When a metal surface is exposed to differential air or oxygen concentrations- forms differential aeration cell. The more oxygenated part of the metal behaves as cathode and less oxygenated part becomes cathode. Differential aeration of metal causes a flow of current called the differential current and the corrosion is called differential aeration corrosion. Example (a): Rusting of an iron. (for reactions refer session-1). Example (b): Consider a piece of Zn metal is partially immersed in a dilute solution of neutral salt (NaCl), and the solution is not agitated properly. The part of the metal above and closely adjacent to the water-line are more oxygenated, because of easy access of oxygen and hence become cathodic. The part of the Zn metal immersed to greater depth, which have less access of oxygen and becomes anode. Hence a difference in potential between the electrodes is created, which causes a flow of Page 73

Differential aeration corrosion     

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current between the two differentially aerated areas of the same metal and causes corrosion at anode. Differential aeration accounts for the corrosion of metals partially immersed in a solution, just below the water line. This type of differential aeration corrosion is also known as water line corrosion. Consider a steel tank containing water. The maximum corrosion takes place along a line just beneath the level of water meniscus. The area above the waterline is highly oxygenated and acts as the cathodic and completely unaffected by corrosion. (Eg. Marine plants attacking themselves in the sides).
Poor oxygenated Area (anode) more oxygenated area (cathode)

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Pitting corrosion is a localised accelerated attack in which only small areas of the metal surface are attacked whilst the remainder is largely unaffected. This localised attack results in pitting. The pits may initiate and propagate to a certain depth resulting in the formation of cavities and becomes inactive. Pitting is very destructive and frequently ruins the tubes, pipes etc.  Pitting is due to breakdown or cracking of the protective film on a metal at specific points. The presence of impurities like sand, dust, scale, etc., on the surface of metal leads to pitting. Corrosion product Anode
More oxygenated cathode

Iron metal

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Pitting corrosion is due to the formation of differential aeration cell. This attack becomes more intensified with time. It is a highly localised attack on the metal. This corrosion occurs only in the presence of specific corrosive environment and the presence of tensile stress on the metal. Stress may be produced on the metal during fabrication of the article or during etching, drawing, servicing etc. This corrosion involves an attack along the narrow paths forming local anodic areas with respect to more cathodic area of the metal surface. The stress produces strains, resulting localised zones, which are chemically active and easily attacked even by a mild corrosive environment results in the formation of fissures. The fissures leads to crack in the presence of stress. The crack grows and propagates perpendicular to the operating stress, and failure occurs after progressing a finite distance. Page 74

Stress corrosion

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

Example: Caustic embrittlement It is a stress corrosion occurring in mild steel when exposed to alkaline solutions at high temperature and stress. The boiler water, usually contains a certain proportion of sodium carbonate added for water softening purposes. In high pressure boilers, the carbonates breaks up to give respective hydroxide and carbon dioxide, and make boiler water alkaline.
Na2CO3+H2O→NaOH+CO2

This very dilute alkaline water flows into the minute hairline cracks and crevices by capillary action. The water evaporates and increases the concentration of the alkali. This concentrates alkali dissolves iron as sodium ferroate in crevices, cracks and the metal under stress. The sodium ferroate decomposes into magnetite and alkali is regenerated in the process as per the following reactions.
NaOH +Fe→ Na2FeO2+H2 Na2FeO2+H2O→ NaOH +Fe3O4

This type of stress corrosion in boilers in the presence of alkaline medium, called caustic embrittlement. This can be prevented by the addition of the substances such as sodium sulphate,
tannin, etc., which blocks the cracks and crevices, thereby prevents the penetration of alkali. Session- 4

Corrosion control Corrosion can be completely avoided only under ideal conditions. Since it is impossible to attain such conditions, it can be minimized by using various corrosion control methods. They are: a) by corrosion inhibitors b) by cathodic protection c) by protective coatings By corrosion inhibitors: Definition: These are the chemical substances (may be organic/inorganic) when added in small quantities to the corrosive environment, forms a protective layer around anodic or cathodic regions by dissolving in the environment and effectively decreases the corrosion rate. Corrosion inhibitors

Anodic inhibitors:  Anions such as tungstates, phosphates, chromates, ions of transitional metals with high oxygen content, are used as anodic inhibitors.  They form a sparingly soluble corrosion product with a newly formed metal ion.  It is adsorbed on the surface of anode forming a protective film and reduces the rate of corrosion.

cathodic inhibitors

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In acidic solutions The reduction reaction involves the evolution of H2 gas. Hence corrosion may be controlled by: 1) Slowing down the diffusion of H+ ions to the cathode, by using organic substances like heterocyclic compounds, urea, amines, thiourea, etc. 2) Increasing the hydrogen over voltage by forming a adherent film of metallic arsenic or antimony at the cathodic area.

In alkaline / neutral solution The reduction reaction involves the absorption of O2 gas. Hence corrosion may be reduced either by removing the oxygen from the corrosive media or by simply decreasing the diffusion rate of oxygen to cathode. 1) The activity of oxygen is reduced by adding chemical substances to the environment around cathode. Ex: sodium sulphite, Hydrazine, etc. 2Na2SO3 + O2→ 2Na2SO4 N2H4 + O2 →N2 + 2H2O 2) By adding the salts such as ZnSO4, MgSO4 etc., into the corrosive medium, the cations of the salts migrate towards the cathode surface and react with OH- ions and forms respective hydroxides on the cathodic region. Zn+2 + 2OH-→ Zn(OH)2 +2 Mg + 2OH-→ Mg(OH)2

Cathodic Protection: The principle is to force the metal to be protected, to behave as cathode. There are two types of cathodic protections namely, 1) Sacrificial anodic protection 2) Impressed current cathodic protection Sacrificial anodic protection  The metallic structure to be protected is connected to a more anodic metal using a metallic wire.  The more active metal gets corroded, while the parent structure is protected from corrosion.  The more active metal so employed is called sacrificial anode.  The sacrificial anodes to be replaced by fresh ones as and when it is required.  Commonly used sacrificial anodes are: Mg, Zn, Al etc.  This method is generally used for the protection of buried pipelines, ship hulls, water tanks, etc. Impressed current cathodic protection  The metallic structure to be protected is made as cathode by impressing the current.  The current is applied in the opposite direction to nullify the corrosion current.  The impressed current is obtained from a source like battery.  An insoluble anode (ex: graphite, high silicon content iron, etc.) is buried in the soil, and connected to the structure to be protected.  The anode is usually placed in a backfill, to provide a better electrical contact with the surroundings.  This method is suitable for large structures and for long term operations.

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Session - 5 Protective coatings     Corrosion is prevented by the application of protective coating on the surface of metal, thereby the metal surface is isolated from the corrosive environment. The coatings being chemically inert to the environment under specific conditions of temperature and pressure, forms a physical barrier between the coated surface and its environment. Coatings are not only prevent corrosion but also decorates the surface of the metal. Important types of protective coatings are: (i) (ii) (iii)  Metal coatings Inorganic coatings and Organic coatings

Metal coatings  Metal coatings can be applied on the base metal by hot dipping process.  This method is used for producing a coating of low melting metals such as Zn, Al, Sn etc., on iron / steel metals which have relatively high melting point.  The process involves immersing of the base metal in a molten bath of coating metal covered by a flux layer.  The flux cleans the surface of the metal base metal and prevents the oxidation of molten coating metal.  The coating metal may be anodic or cathodic to the base metal.  Example: Galvanising and Tinning Galvanising Coating of zinc on iron or steel, by hot dipping process is called galvanising. (M.P of Zn = 419oC) The article is washed with organic solvents to remove oil/grease, with sulphuric acid to remove scale/rust, then with water and dried, before coating. Coating metal is anodic to iron/steel, called anodic coating. The molten metal bath is covered with a flux of Ammonium chloride, which prevents the oxidation of the coated metal. The article is dipped in a molten bath of Zn. The excess of coated metal is removed by passing through a pair of hot rollers and cooled gradually. Galvanising is applied to nails, bolts, Tinning Coating of tin on iron or steel, by hot dipping process is called tinning. (M.P of Sn = 232oC). The metal surface is washed with organic solvents to remove oil/grease, with sulphuric acid to remove scale/rust then with water and dried, before coating. Coating metal is cathodic to iron/steel, called cathodic coating. The molten metal bath is covered by a flux of Zinc chloride. The clean and dry sheet is passed through flux layer, molten tin, finally removed out through palm oil, which prevents the oxidation of the coated tin. It possesses more resistance against atmosphere. It is non-toxic in nature and more noble Page 77

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pipes, roofing sheets etc.  Galvanised sheets cannot be used for  preparing/storing food stuffs, since Zn dissolves in acidic medium and forms toxic compounds.  If any crack is produced on the galvanised sheets, causes severe  corrosion on the coated Zn metal and the base metal is protected.  Zn is chosen as a protective coating for  iron/steel because of its natural resistance against corrosion in most atmospheric conditions, and Zn is electronegative to iron and can protect it sacrificially. 

than the base metal. Tinning is widely used for coating the steel sheets, Cu and brass sheets used for manufacturing containers for storing/packing food materials, cooking utensils, refrigeration equipments, etc. If any crack is produced on the tinned sheets, causes severe corrosion of the base metal. Tin coatings form a useful preparation for protective painting in general applications.

Inorganic coatings (Chemical conversion coatings)  These coatings are produced at the surface of the metal by chemical / electrochemical reactions.  These coatings are applied on the article for decorative effect and to increase the corrosion resistance of the base metal.  These serves as an excellent base coating for paints and enamels.  Examples: Anodising and Phosphating

Session-6 Anodising Phosphating  These coatings are generally produced  These coatings are generally applied on non-ferrous metals like Al, Zn, Mg frequently to iron, steel and zinc and to and their alloys by anodic oxidation a lesser extent on Al, Cd and Sn. (electrochemical) process.  These are produced by the chemical  The base metal is made as anode. reaction of the base metal with  Anodising of Al: It is carried out to aqueous solution of phosphoric acid produce a porous/nonporous coating. and phosphate of Fe, Mn or Zn. The porous coating is obtained by  The reactions are slow, hence it is anodic oxidation. The electrolysis is enhanced by using accelarators along conducted in an acid bath, at moderate with the phosphating mixture. temperature 30-40oC, using moderate  The most common mode of current densities, in which the base metal is acceleration is by addition of oxidizing made as anode. The commonly used baths agents, such as nitrate, nitrite, chlorate are H2SO4 / Chromic acid / Phosphoric acid and hydrogen peroxide. /oxalic acid. The thickness of the film  The chemical reaction between the increases with progressive oxidation. Outer base metal and the phosphating most layer of the oxide film is very porous mixture results in the formation of and soft, these pores are sealed by surface film consisting of crystalline exposing to the boiling water. In this Mn-Fe Phosphate, Zn-Fe Phosphate
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process the metal oxide layer changes into its mono hydrate. The non porous coatings are produced  by using non-corrosive electrolytes like boric acid and borax. These coatings are applied on electrolytic condensers.   The anodised coatings are thicker than the natural oxide film and possess improved corrosion resistance as well as resistance to mechanical injury.  Organic coatings

etc. These coatings are applied by immersion or spraying or brushing. These coatings do not offer complete resistance to the atmospheric corrosion. These are used as a primer coat for paints, enamels, etc.

 Organic coatings acts as inert organic barriers between the surface of the metals and corrosive environment.  The coating formed on the surface of the metal must be cohesive, continuous and non-porous.  These coatings resists corrosion and they are decorative. Various colouring matters are added to these coatings, gives a pleasing effect.  Few important groups of organic coatings are paints, enamels, varnishes, etc.  Paints: Paint is a mechanical mixture consisting of pigments and fillers or extenders suspended in a vehicle. Vehicle is a film forming drying oil. Other liquids called thinners or diluents are added to the oil. Thinners are volatile organic solvents such as acetone, xylol, turprntine, etc.  Paint is usually applied to the surface of the metal by spraying or brushing. The thinner evaporates. The drying oil is slowly oxidized, a dry pigmented film is formed on the surface.  Requisite properties of a good paint: a) b) c) d) e) Paint must have high covering power and adhesion capacity. It must form a tough, uniform coherent film. It must resist corrosion. Film must not get cracked during drying. Colour should be stable, glossy and washable.

 Constituents of paint: Constituent Pigment Requisite property It must be opaque, must have good covering power. Must be chemically inert and stable. Must be non-toxic, cheap and easily available. It must freely mix with film forming constituents. Function UV light catalyses the destructive oxidation of a paint film, pigments reflects UV light and protects the film. Increases the strength of the film Gives good colour and opacity Example ZnO, TiO2, Fe2O3, PbCrO4, etc.

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Pigments are held on the surface due to vehicle. Film is formed due to oxidation and polymerization of unsaturated constituents present in it, followed by the evaporation of oil. It must reduce the Dissolves additives in the Thinners viscosity of the paint. vehicle. Increases the elasticity of the film. Increases the penetration power. Driers are oxygen It must accelerate the To improve the drying carrier catalysts. drying process through quality of the film. oxidation, polymerization and condensation. . Vehicle (medium): It is a film forming drying oil, esters of glycerol having high Mol.wt.

It must make the film tough. It should increase the durability of the film. It must make the film formed to be water proof.

Linseed oil, soyabean oil, dehydrate caster oil, etc. Turpentine, xylol, benzene

Resinates, linoleates, tungstates of Co, Mn, Pb and Zn. To provide elasticity and to Tricresyl Plasticizers minimize its cracking phosphate, triphenyl phosphate, etc. Extenders are low To reduce cost, to Act as carriers for the Magnesium refractive indices increase durability of the pigment. silicates, materials. paint, to reduce cracking baryta, of film. calcium carbonate, etc. Enamels Enamel is a pigmented varnish. It gives lustrous, hard and glossy finish to the film. The important constituents of enamels are pigments, vehicle, driers and thinner. These are used for painting metallic surfaces like bicycles, electrical devices, etc. Questions 1) 2) 3) 4) 5) 6) 7) What is corrosion? Discuss the electrochemical theory of corrosion. Discuss the various factors that influences the rate of corrosion. What is sacrificial anode? How corrosion can be controlled by sacrificial anodic protection? What is meant by differential aeration corrosion? How can it be prevented? Explain the impressed current cathodic protection. What are corrosion inhibitors? Classify different types of inhibitors with examples. Discuss in detail about chemical conversion coating. Page 80

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8) 9) 10)

State the characteristics of a good paint. What is a paint? What are the constituents of a paint and explain their functions? Write a note on: (i) Galvanic corrosion (ii) Pitting corrosion (iii) Waterline corrosion (iv) Stress corrosion (v) Organic coatings (vi) Anodising of Aluminium (vii) Galvanizing (viii) Tinning.

REFERENCES: 1) Engineering Chemistry by Jain & Jain. 2) An Introduction to Metallic Corrosion by Wranglen G.

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Metal Finishing
Session -1 Introduction The materials such as metals/alloys are required for various engineering applications. These materials should be ideal and must meet several requirements like resistance to corrosion, wear resistance, mechanical properties, etc. It is impossible to have all these properties in a single metal. Hence, to improve the lacking properties in these materials, metal finishing is one of the methods employed for the purpose. Metal finishing is the process carried out to modify the surface properties of a metal by electro deposition of a layer of another metal on the substrate. Technological importance of metal finishing Metal finishing is important for a decorative appearance, also to enhance the surface properties. The technological importance of metal finishing is in importing certain properties in addition to their original properties. The important properties are:
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Corrosion resistance Wear resistance Electrical resistance Chemical resistance Reflectivity and appearance (e.g., brightness or color) Solderability Ability to bond to rubber (e.g., vulcanizing) Hardness, etc.

Important techniques of metal finishing are:    electrolytic plating, electroless plating, and chemical and electrochemical conversion processes

The supporting processes include degreasing, cleaning, pickling, etching and polishing. Some of the materials used in metal finishing are: solvents and surfactants for cleaning, acids and bases for etching, and solutions of metal salts for plating the substrate. The metal finishing generally categorizes plating operations as electroplating and electroless plating. Significance of factors governing the process of electrolysis: The important factors that control the process of electrolysis in electroplating are:
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(i) Polarization, (ii) Decomposition potential and (iii) Over voltage. Polarization During electrolysis, the electrical energy supplied by the external source is converted into chemical energy. When the current is passed through an electrolytic bath, the electrolyzed products deposit on the surface the electrodes. Hence, the passage of current gradually decreases and falls almost to zero. This is due to back e.m.f. which drives the current in the opposite direction to which imposed current flows from the battery. This phenomenon of setting up of back e.m.f. during electrolysis is called ―Polarization‖ and the current developed is called polarization current. The polarized voltaic cell is called a secondary cell. Due to polarization, the rate of diffusion of reactants/products on to the surface of the electrodes decreases. The more adherent and non-porous the film formed, the more it contributes to the increase of polarization at an electrode. These are of considerable importance in determining the rate of corrosion of a metal. Decomposition potential The electrolysis cannot be carried indefinitely unless the back e.m.f. due to polarization is overcome. The applied voltage is gradually increased, till a point is reached at which the electrolysis again begins and proceeds continuously. This happens when applied e.m.f. is just sufficient to overcome the back e.m.f. The minimum voltage required to bring about the electrolysis without any interruption is called ―Decomposition potential‖. The decomposition potential depends on the nature of the solution and electrode material. If the metal has higher solution pressure, the electrode tries to send the ions back into the solution more easily. Therefore it is more difficult to deposit that metal i.e., it has a higher decomposition potential. For example, solution pressure of Zn is more than that of Cu. It is found that Zn has higher decomposition potential (2.55V) than that of Cu (1.5V). If the applied e.m.f. is less than 2.55V and more than 1.5V between the Cu electrodes, only Cu will be deposited on the cathode while Zn remains in the solution. Thus if the difference in decomposition potentials is large, metals may be separated. Hence, knowledge of decomposition potential is important in electro refining, electro metallurgy, etc.

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c u r r e n t Decomposition potential

Voltage

Session -2 Over Voltage It was observed that during electrolysis back emf arises and a minimum voltage is to be applied for continuous electrolysis. If the back emf is overcome, electrolysis must proceed. This back emf may be calculated by considering the cell set up by the products of electrolysis and it is equal to the emf of the reversible cell at one atmosphere. When this emf is compared with the decomposition potential, it is found that the value is higher than the required emf value. This difference between the observed voltage and the theoretical voltage is known as over voltage. Over voltage depends on nature of electrode, physical state of the substances deposited, current density and temperature. It is due to surface phenomenon. It depends on how ions are discharged and the rate at which they are discharged. Hydrogen over voltage is of particular significance in many electrolytic reactions and especially in electroplating and corrosion. Electroplating        Electroplating is achieved by passing an electric current through an electrolytic solution containing metal ions and the electrodes. The metal object to be plated, serves as cathode in an electrolytic cell and attracts metal ions from the solution. In an electrolytic bath, the coating metal or an inert material of good conducting capacity, may be used as anode. If the anode used in electrolysis is other than the coating metal, the salt to be added continuously to the electrolytic bath in order to maintain the optimum metal ion concentration in the solution. Ferrous and non-ferrous metal objects are plated with a variety of metals including aluminum, brass, bronze, cadmium, copper, chromium, gold, lead, nickel, platinum, silver, tin, etc. The process is regulated by controlling a variety of parameters including voltage, temperature and purity of bath solutions. Plating baths are almost always aqueous solutions, therefore, only those metals that can be reduced in aqueous solutions of their salts can be electrodeposited. Page 84

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

A good deposit should be continuous, uniform, non-porous, bright, lustrous, hard and ductile.

Factors influencing the nature of the deposit Various factors which affect the nature of an electro deposit are: 1. 2. 3. 4. 5. 6. Composition of the electrolytic bath Additives Current density Temperature pH of the bath and Throwing power of the plating bath

Composition of the electrolytic bath:   The metal salt used for the preparation of the electrolytic bath must be highly soluble, good conductor and should not undergo any chemical transformation like hydrolysis, reduction etc. in the bath during electrolysis. To get very adherent and thin coating films, low metal ion concentrations are preferred.

Additives:   These are the substances added to the bath to improve the nature of the deposit, they are complexing agents, brighteners, levelers, wetting agents, structure modifiers, and pigments. Complexing agents are added to maintain low metal ion concentration in solution, to improve throwing power of the plating bath, to increase the solubility of the sparingly soluble salts and to avoid the passivity of anode. The most commonly used complexing agents are hydroxide, cyanide and sulphomate ions. Brighteners are the chemical substances added to get bright and lustrous deposit, for example: sodium formate, coumarin, thiourea, cobalt sulphonate, etc., are added as brighteners in Ni plating. The concentration of these brighteners must be maintained in the optimum range, otherwise results a fine grained deposit. Levelers are the substances helps to form a uniform deposit on the surface by preferential adsorbption at the places where rapid deposition of the metal takes place. Many brighteners also behave as levelers. Structure modifiers: These are also called as stress relievers. These substances alter the structure of the electrodeposit and thereby modify the properties of the electrodeposit. Wetting agents are used to remove the adsorbed hydrogen from the cathode, otherwise it may lead to pitting. Pigments are added to get pleasing color on the surface of the substrate.

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Current Density:   It is the current / unit area of substrate surface. It is expressed in mA cm-2 or A m-2 If current density is high, results loose and brittle deposit. If current density is low, takes long time for electroplating, since the rate of electro deposition is low. Hence optimum current density should be employed.

Temperature:     The increase in temperature increases the solubility of the dissolved salt and also increases the diffusion of the ions. Therefore, the time required for the process reduces. With increase in temperature, the rate of evolution of hydrogen gas at cathode increases, results the spongy and loose deposit. At low temperature, electroplating results a powdery, non-coherent deposition. Therefore moderate temperature is preferred.

pH of the bath:    If the medium is acidic, the hydrogen evolution takes place at cathode and affects the nature of the deposit. At higher pH values, the insoluble metal hydroxides deposits on the article. Therefore appropriate pH must be maintained by using buffer.

Throwing power of the plating bath:
 

Throwing power is the ability of a plating bath to deposit a uniform thickness of metal from high-current-density areas to low-current-density areas. It can be determined by Harry-Blum cell as shown below. It consists of two cathodes (insulated) and an anode at the centre. Two cathodes are at different distances d1 and d2 from anode (let d1>d2). The cell contains plating bath solution whose throwing power is to be determined.
+

d1 Cathode1

d2

Cathode2

Electrolytic solution

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

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The process of electroplating is carried out and the weights (w1 and w2) deposited at cathodes are noted. 100( x  y) The % of throwing power = ; where x=d1/d2 and y=w1/w2; (w1>w2). ( x  y  2)

Session -3

Surface preparation: It is very much necessary to clean the surface of the base metal before electroplating in order to get a good deposit. The impurities found on the surface may be grease, oxide film, oil, dust, etc. Various methods available to clean the surface of the metal are:        Solvent cleaning: Organic solvents (acetone, ether, etc) are used to remove impurities like oil, grease, etc., from the metal surface. Alkali cleaning: This is employed to remove old paint from the metal surface by using solutions of NaOH, sodium silicate, sodium carbonate etc. Acid cleaning: It is used to remove oxides and other contaminants from the metal surface. Mechanical cleaning: is used to remove loose rust and other impurities from the surface. Strong adhering scales are removed by using grinding wheels, knife, etc. Pickling: This is used to remove oxide scale from the surface by dipping in dilute HCl or H2SO4. Flame cleaning: is employed to remove moisture from the metal surface. After cleaning the metal surface by the above method, essentially the metal should be rinsed with water.

Electroplating of Cr, Ni and Cu A well cleaned and pre treated surface of material to be electroplated for long life and for decoration purposes. The electroplating of Chromium, nickel and copper are as follows:

Chromium plating Anode

Decorative chromium Hard chromium Insoluble anodes like Pb, Pb- Insoluble anodes like Pb, Pb6% antimony, Pb-7% Sn, etc. 6% antimony, Pb-7% Sn,etc. Object to be plated Object to be plated 100:1 chromic acid and H2SO4

Cathode 100:1 chromic acid and H2SO4

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Bath composition Current Density (mA cm-2)

145-430

290-580

45-55 oC Temperature 10-15 Current Efficiency (%) Applications

45-55 oC 17-20

provides durable and good Extensively used in industrial finish on automobiles, surgical and engineering applications. instruments etc.

Nickel plating is mostly applied on iron. Since nickel is cathodic to iron, the coating must be of sufficient thickness; otherwise it leads to severe corrosion.

Nickel plating Anode

Sulphate bath Sulphamate bath Ni pallets in titanium mesh Ni pallets in titanium mesh basket basket Article to be coated Article to be coated

Cathode 250g NiSO4 +45g NiCl2+30g 600g Ni sulphamate+5g NiCl2 Bath composition per boric acid. +40g boric acid.
liter

20-50
Current Density

50-400 98

Current Efficiency(%) Additives

95

Cd salts, glucose gives bright naphthalein-1,3,6-trisulphonic deposit. acid 35-40 oC 50-60 oC 4

Temperature pH Applications Electrode reactions

4.5 - 5

used as an undercoat for Cr Decorative purposes plating. At anode: Ni→Ni+2 +2eAt cathode: Ni+2 +2e-→Ni

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Copper plating Anode Cathode

Cyanide bath Pure Cu The article to be coated

Acid Sulphate bath Pure Cu The article to be coated

Bath composition per 45g of CuCN + 25g of 240gCuSO4+75gH2SO4 liter. NaCN+10g of Na2CO3. Current Density 10-40 mA/cm2 20-40 mA/cm2 Current Efficiency (%) 60-90 95-98 Additives Temperature pH Applications sodium thiosulphate Gelatin 40-50oC 15-20oC 12-13 4-4.5 As an under coat for Cr plating and PCB (suitable for iron and In PCB (not suitable for iron its alloys plating) and its alloys plating) +2 At anode: CuCu +2e At cathode: Cu+2 +2e-Cu

Electrode reactions

Session -4 Electroforming     Electroforming is a highly specialized process for fabricating a metal part by electrodeposition in a plating bath over a base form or mandrel. The advantage of the electroforming process is that electroformed metal is extremely pure, with superior properties over wrought metal due to its refined crystal structure. Multiple layers of electroformed metal can be molecularly bonded together. In comparison with other fabrication methods, Electroforming is essentially insensitive to temperature or humidity, electroformed parts have excellent light transmission when used in optical application, electroformed parts have very low mass, electroformed parts are electrically conductive and essentially unbreakable.

Electrochemical Machining (ECM) is an important method for removing metal by anodic dissolution in a conducting electrolyte. ECM is a relatively fast method, with important advantages over more traditional machining methods (mechanical, laser,
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electrochemical discharge) since it can be applied to any electrically conductive material regardless of its hardness. Also there is no need to use a tool made of a harder material than the workpiece. Moreover, ECM is able to produce smooth, stress and crack free surfaces, which is of major importance for workpieces which have to function in extreme environments (temperature, pressure, etc.). Electrochemical etching of metals is somehow related to ECM since it involves the selective removal of metal from an initial metal foil or predeposited metal layer. The metal is covered with a photoresist layer (photosensitive surface) and is selectively exposed to a UV light source. The photoresist on the exposed areas is removed by a chemical agent and subsequently the exposed areas are electrochemically etched. The applications are mainly in the micro-structure domain. Electropolishing is an important method for imparting brilliance by removing a thin layer of the surface. It is analogous to a reverse electroplating process without any working of the underlying metal. This is also known as a bright finishing. The process highlights surface irregularities (i.e. roll grit pattern, pickle matte, scratches, pits and digs). Electroless Plating   Electroless plating is a technique of depositing a noble metal from its solution on a catalytically active surface of the substrate without using electrical energy. The basic ingredients in an electroless plating solution are (i) soluble salt of metal, (ii) a reducer (causes the reduction of metallic ions to metal), (iii) a complexing agent (improves the quality of the deposit), (iv) stabilizer (to prevent decomposition of the plating bath solution), (v) Exaltant (to increase the plating rate) and (vi) buffers (to maintain pH) and other chemicals designed to maintain bath stability and to increase bath life. The driving force is autocatalytic redox reaction on pretreated catalytic surface. The active surface of the object to be cleaned before plating. Electroless plating commonly generate more waste than other plating techniques, but it vary significantly in efficiency. Even irregular shapes can also be plated uniformly. Example: Electroless plating of Cu commonly used for printed circuit boards.

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Distinction between electroplating and electroless plating

Property

Electroplating

Electroless plating

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Source

Electrical energy is obtained No electrical energy is required from external source.

Anodic reaction takes place at Site of anodic separate anode used in the The site of anode reaction is the electrolytic cell. reaction. article to be plated. Article to be plated acts as cathode Site of cathodic metal reaction. Anode Type of deposit obtained Pure Catalytic surface on the article to be plated Reducing agent in solution Contaminated

Plating is carried out on Type of cathode metals. used for plating Plating may be carried out on insulators (ex: plastics) and semiconductors. At anode: M M+n + neReactions At anode: Reducing agent  Oxidised product + neAt cathode: M+n +ne-M At cathode: M+n +ne-M

Session -5 Advantages of electroless plating (i) No electrical power is required, (ii) plating may also be obtained on insulators and semiconductors, (iii) better throwing power compared to electroplating, (iv) these coatings possess unique mechanical, chemical and magnetic features.

Electroless Plating of copper on PCB  The surface to be coated must be cleaned properly by using organic solvents, followed by acid treatment.

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    

Non-metallic materials like glass, plastics, PCB, etc., are activated by dipping in the solution containing SnCl2 and HCl, followed by dipping in palladium chloride solution. On drying the surface it is found to have a thin layer of Pd. The composition of the bath is: 12g/L CuSO4(coating solution), 8g/L formaldehyde (reducer), 15g/L NaOH + 14g/L rochelle salt (buffer), 20g/L EDTA (complexing agent and exhaultant). pH is to be maintained around 11 and the optimum temperature is 25 oC. Reactions are: At anode: HCHO + OH- HCOO- +2H2O +H2+2eAt cathode: Cu+2 +2e-  Cu. Net redox reaction: HCHO + OH-+ Cu+2 HCOO- + 2H2O + H2 + Cu Copper ions are consumed in the reaction are to be replaced periodically.



Typical application of electroless copper plating is PCB: The process involved is known as substractive method. A thin layer of copper is first coated over the PCB (may be glass reinforced/ GR-P/ phenolic polymer). The selected areas are protected by employing electroplated image (or photoresist) and the remainder of the plated copper is etched away so as to get required type circuit track. More number of components may be packed in a small space by making double sided tracks. The connection between the two sides of PCB is provided by drilling holes, followed by electroless Cu plating through holes.

Electroless nickel Plating

  

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The metal surface is first cleaned by using organic solvents followed by acid treatment. Aluminum can be directly plated without any activation. The electroless bath consists of coating solution of NiCl2 (20 g/L), sodium hypophosphite as a reducing agent (20 g/L), sodium acetate buffer (10g/L), sodium succinate behaves as a complexing agent and exhaultant, pH is maintained around 4.5 and the temperature is around 93oC. The electrode reactions are: At anode: NaH2 PO2 + H2 O NaH2 PO3 + 2H++2eAt cathode: Ni+2 +2e-  Ni Net redox reaction : NaH2 PO2 + H2 O+ Ni+2 NaH2 PO3 + 2H++ Ni

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The H+ ions are released in the above redox reaction, decreases the pH of the medium. This affects the quality of the deposit. Therefore, addition of buffer is very essential to maintain the pH. Further, Ni+2 ions and sodium hypophosphite are consumed during the redox reaction, hence it should be replenished periodically. Advantages: (i) (ii) (iii) (iv) Possesses excellent throwing power, hence method is suitable for plating the objects having intricate shapes. The deposits are free from pores, hence possesses better corrosion resistance. The plating gives harder surface, hence it gives good wear resistance. This plating on Al enhances the solderability, also provides a nonmagnetic underlay in magnetic components.



Applications: (i) (ii) (iii) (iv) Electroless Ni plating is extensively used in electronic appliances Electroless Ni plating is used in domestic as well as automotive fields. Electroless Ni plated polymers are used for decorative purposes. Electroless Ni plating is also preferred in hydraulic compressors, pressure vessels, pumps, etc.

References: 1. Electroplating by Frederick A. Lowenheim 2. Engineering Chemistry by Jain and Jain

Questions 1. Write a note on: (i) Polarisation, (ii) Decomposition potential and (iii) Over voltage. 2. Write a note on ―Technological importance of metal finishing‖. 3. Describe the various methods used for surface preparation. 4. Distinguish between electroplating and electroless plating 5. Give an account on Electroplating. 6. Explain Electroless plating of Cu on PCB and Ni on Al. 7. Write a note on Electroplating of copper. 8. Give a brief account on composition of electroless plating

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Water pollution
Session - 1 Introduction Water exists in three states: solid, liquid and gaseous. The important sources of water are (i) rain water, (ii) ground water and (iii) sea water. Rain water carries the washed out minerals, salts and organic matter from the earth‘s surface and stores them in ponds, lakes and rivers. It seeps into underground and is stored as ground water. Sea water is highly alkaline due to the presence of dissolved salts. The natural water contains numerous organisms and dissolved gases (ex: oxygen), which is essential for aquatic organisms. The pure water is one which is free from organisms. Water is required mainly for drinking and cooking, also for industry, agriculture and many other activities. Pollution of water implies that it contains a lot of inorganic and organic substances introduced by human activities, which change its quality, not suitable for any purposes and also harmful for living organisms. (or) Any alteration in physical, chemical or biological properties of water, as well as the addition of any foreign substance makes it unfit for health and which decreases the utility of water, is known as water pollution.   The substances which cause pollution are called pollutants and the common pollutants which are present in water are (i) Suspended solids (ii) Organic matter, (iii) Inorganic pollutants, (iv) Oil, etc. Turbidity in water is mainly due to; (i) finely divided undissolved solids, clay, slit; (ii) colloidal particles and (iii) organic matters. Turbidity gives unsightly appearance. When it is used in industries, it causes problems in functioning of equipments, boilers, etc. This can be removed from water by applying proper treatments like settling, coagulation (by using alum) and filtration. Organic pollutants include domestic and animal sewage, biodegradable organic compounds, industrial wastes, synthetic pesticides, fungicides, herbicides, detergents, oil, grease, pathogenic microorganisms, etc. It results in rapid depletion of dissolved oxygen of water and thus such water becomes harmful for aquatic lives. Organic matter present in water can be removed by using chlorination, coagulation and ultra filtration processes. Inorganic pollutants consist of mineral acids, inorganic salts, finely divided metals, cyanides, sulphates, nitrates, organometallic compounds, etc. Oil and grease constitutes important water pollutants. These substances coat ion exchange resin, causes premature exhaustion of beds. It can be removed by coagulation with alum.

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Main sources of water pollution are (i) domestic and municipal sewage; (ii) industrial waste; (iii) agricultural waste; (iv) radioactive materials, etc.  Domestic sewage consists of human excreta, street wastes, organic substances that provide nutrition for bacteria and fungi. It is grey green or grey yellow in color and darkens with time due to decomposition, when becomes stale it develops offensive odor due to evolution of gases like NH3, H2S, etc. It is normally turbid Page 95

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due to the presence of suspended solids. Its temperature is slightly higher than ordinary water. These pollutants cause many hazardous effects on health. Discharge of sewage in river and lakes spreads water borne diseases. A pollutant present in industrial waste water damages biological activities and kills many useful organisms. Most of the industrial wastes dissolved in water are particulate in nature and are present at the bottom of the water system. These acts as poison for the aquatic organisms. Further, toxic metals present in industrial effluents are extremely hazardous for living beings. Agricultural discharge consists of pesticides, fertilizers, insecticides, etc. In agriculture in order to increase the production and to escape the crops from various diseases, the fertilizers and insecticides are used. Any substance or a mixture of substances which prevents, repels, destroys any pest is called a pesticide. These pollutants contaminate the water and when this is used by human being, affect the oxygen carrying capacity of hemoglobin and consequently causes suffocation and irritation to respiratory and vascular system. Radioactive wastes are mainly from atomic explosion and processing of radioactive materials near the source of water. The other sources are waste from hospitals, research laboratories, etc. The radioactive pollutants in water cause serious skin cancer, carcinoma, leukemia, DNA breakage, etc. Water pollution by heavy metals: About 70 metallic elements are called heavy metals, as they have atomic numbers of 22 to 92 and atomic weight higher than that of sodium and with a specific gravity of more than 5.0. Only a few of these heavy metals are considered potentially damaging to living systems.

Session - 2 Sources and ill effects of heavy metals and inorganic species Heavy Metal Cd Sources Their effects

Hg

Pb

Discharges from electroplating Gets adsorbed on suspended matter in industries, Battery manufacturing the water, when it is consumed causes units, metallurgical industries, etc. liver and kidney necrosis, increased salivation nausea, acute gastritis, etc. Effluents from chloro-alkali Mercury poisoning causes kidney industries, pesticide industries, damage, and exhibits the symptoms like Chemical industries, etc. numbness in the limbs, muscles, blurred vision leading to blindness, emotional disturbances etc. It also damages brain and nervous system, and paralysis followed by death. Electric storage battery industries, A cumulative poison causing loss of petroleum industries, ceramic apatite, constipation, abdominal pain, industries, electric cable insulation, mental retardation, nervous disorder and paint industries, plastic industries, brain damage. pesticides, pipe-manufacturing units, etc. Page 96

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NH3 H2S

Metal finishing and cleaning, electroplating, coke ovens and many other industrial processes generate cyanide and discharge as effluent to water bodies. Ammonia is generated by the biological decay, reduction of nitrates under anaerobic conditions. By bacterial reduction of sulphate and decomposition of organic matter.

Cyanide is extremely toxic. Exposure even to small quantities over longer periods causes loss of apatite, dizziness, etc. In high concentration, it is toxic to fish and other aquatic organisms. It imparts characteristic odor to water. Causes corrosion, imparts bad odor.

Sewage treatment The polluted water is characterized by its oxygen demand and solid content. The biological oxygen demand (BOD) measures the level of organic pollution in the sewage water. The sewage must be treated before being discharged into the water bodies. The treatment is carried out in three stages- primary, secondary and tertiary. (i) In primary treatment, the suspended solids and floating objects are removed using coarse screens and sieves. (ii) In secondary treatment, the maximum proportions of the suspended inorganic/ organic solids are removed from the liquid sewage. The liquid material passes into the sedimentation tank and finely suspended particles are allowed to settle by adding coagulants like Alum. The suspended materials settle down in the tanks and forms sludge. The sewage water after sedimentation process is allowed for aerobic oxidation. The organic matter is converted into CO2, the nitrogen into NH3 and nitrites to nitrates. The treatment is carried out by activated sludge process. The above process is based on the principle that if an adequate amount of oxygen / air is passed through the sewage containing aerobes, complete aerobic oxidation occurs. This oxidation process becomes speedy by the addition of a part of sludge from the previous process, called activated sludge. Settled sludge is sent back for feeding fresh bulk of sewage, while the remainder is disposed off by land spreading, sea burial etc. (iii) Tertiary treatment is applied to remove detergents, metal ions, nitrates and pesticides, as these are not removed in the earlier treatments. The phosphates are removed as calcium phosphates by adding calcium hydroxide at pH 10-11. At this pH, ammonium salts are also converted into ammonia. Fine particles are further removed by sedimentation in the presence of coagulants. The effluent is chlorinated to remove pathogenic bacteria‘s and finally passed through activated charcoal to absorb gases. The treated water is of high clarity, free from odor and low BOD, therefore it is nearly equivalent to drinking water. Session -3 BIOLOGICAL OXYGEN DEMAND
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It is defined as the amount of oxygen required for the biological oxidation of the organic matter under aerobic conditions at 20oC and for a period of 5 days. Characteristics of BOD  It is expressed in parts per million (ppm) or mg/dm3.  Larger the concentration of decomposable organic matter, greater is the BOD and consequently more is the nuisance value.  Strictly aerobic conditions are required.  Determination is slow and time consuming. Determination BOD      The method is based on the determination of dissolved oxygen before and after 5 days period, at 20oC. A known volume of sample of sewage is diluted with known volume of water containing nutrients for bacterial growth, whose dissolved oxygen content is predetermined. The whole solution is incubated in a closed bottle at 20oC for 5 days. After incubation the unused oxygen is determined. The difference between the original value of oxygen content in the diluted water and unused oxygen of solution after 5 days gives BOD.

CHEMICAL OXYGEN DEMAND (COD) COD is a measure of oxidisable sewage. It includes both the biologically oxidisable and biologically inert matter such as cellulose, as a result of which the value of COD is more than BOD. COD is defined as the amount of oxygen (in ppm) consumed under specified conditions, while oxidizing total organic load of the sample with a strong oxidizing agent (Ex: potassium dichromate) in the acid medium. Determination COD     A definite volume of waste water sample (‗x‘ ml) is refluxed with a known volume of K2Cr2O7 in H2 SO4 medium in the presence of AgSO4 (which acts as a catalyst) and HgSO4 (which eliminates interference due to chlorine). K2Cr2O7 oxidises all organic matter into water, CO2 and ammonia. The unreacted dichromate is titrated with a standard solution of ferrous ammonium sulphate (FAS) (Let the volume consumed is v2 ml). (v  v ) N  8  1000 COD = 1 2 FAS ; v1 corresponds to the volume of FAS consumed x in the blank titration (i.e., in the absence of waste water sample).

REFERENCE Environmental pollution by M.C. Dash. Problems 1. Calculate the COD of the effluent sample when 25 ml of an effluent requires 8.3 ml of 0.001M K2Cr2O7 for oxidation. [Given molecular mass of K2Cr2O7 =294).

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Solution: Given Concentration of K2Cr2O7 =0.001M Molecular mass of K2Cr2O7 =294 Volume of the effluent sample =25 ml Volume of the K2Cr2O7 consumed by the effluent =8.3ml (i) 1000ml of 1M K2Cr2O7 =294 g 8.3 ml of 0.001M K2Cr2O7 = (294×8.3×0.001)/1000 Amount of K2Cr2O7 present =2.4402mg 1mol of K2Cr2O7  6 equivalents of oxygen i.e., 294 mg of K2Cr2O7  6×8 mg of oxygen 6  8  2.4402 =0.3984 mg  2.4402 mg of K2Cr2O7  294 COD in 25 ml of water =0.3984 mg 1000ml of water =398.4/25=15.92 mg  COD of water=15.92 mg/dm3

(ii)

(iii)

2.

What would be BOD value for a sample containing 200mg/dm3 of glucose assuming that it was completely oxidized in the BOD test? (Atomic wt. of C=12; H=1; O=16). C6H12O6+6O26CO2 +6H2O Molecular mass of glucose = 180 g From the above equation, 180g of glucose requires 192 g of oxygen 192  200 =213.33 mg  200 mg of glucose  180 -----------xxx----------

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